Edge-bridged Double Cubane Research Articles

An Iron-Sulfur Cluster with a Highly Pyramidalized Three-Coordinate Iron Center and a Negligible Affinity for Dinitrogen.

Attempts to generate open coordination sites for N2 binding at synthetic Fe-S clusters often instead result in cluster oligomerization. Recently, it was shown for Mo-Fe-S clusters that such oligomerization reactions can be prevented through the use of sterically protective supporting ligands, thereby enabling N2 complex formation. Here, this strategy is extended to Fe-only Fe-S clusters. One-electron reduction of (IMes)3Fe4S4Cl (IMes = 1,3-dimesitylimidazol-2-ylidene) forms the transiently stable edge-bridged double cubane (IMes)6Fe8S8, which loses two IMes ligands to form the face-bridged double-cubane, (IMes)4Fe8S8. The finding that the three supporting IMes ligands do not confer sufficient protection to curtail cluster oligomerization prompted the design of a new N-heterocyclic carbene, SIArMe,iPr (1,3-bis(3,5-diisopropyl-2,6-dimethylphenyl)-2-imidazolidinylidene; abbreviated as SIAr), that features bulky groups strategically placed in remote positions. When the reduction of (SIAr)3Fe4S4Cl or [(SIAr)3Fe4S4(THF)]+ is conducted in the presence of SIAr, the formation of (SIAr)4Fe8S8 is indeed suppressed, permitting characterization of the reduced [Fe4S4]0 product. Surprisingly, rather than being an N2 complex, the product is simply (SIAr)3Fe4S4: a cluster with a three-coordinate Fe site that adopts an unusually pyramidalized geometry. Although (SIAr)3Fe4S4 does not coordinate N2 to any appreciable extent under the surveyed conditions, it does bind CO to form (SIAr)3Fe4S4(CO). This finding demonstates that the binding pocket at the unique Fe is not too small for N2; instead, the exceptionally weak affinity for N2 can be attributed to weak Fe-N2 bonding. The differences in the N2 coordination chemistry between sterically protected Mo-Fe-S clusters and Fe-only Fe-S clusters are discussed.

Nitride-incorporated W-Fe-S double cubane clusters: terminal ligand substitutions and redox behaviors.

Structural mimicking of the nitrogenase FeMo cofactor has long been a challenge in synthetic inorganic chemistry and bioinorganic chemistry. This already very tough task had become even harder after the discovery of an interstitial light atom, which was later evidenced to be carbide. From a synthetic point of view, to introduce such a 2p atom into the core of a Fe-S cluster would have to overcome the coordination competition from overwhelming sulfide ligands. Recently, we have reported a controlled synthetic strategy named redox metathesis based on template-assisted structure design, and have successfully synthesized a couple of nitride-incorporated edge-bridged double cubane (N-EBDC) W-Fe-S clusters. In this work, we have systematically studied the terminal ligand substitutions of heteroleptic N-EBDC clusters, utilizing ethanethiolate, thiophenolate, p-thiocresolate, azide, and methoxide to replace the terminally bound chloride ligands. Structural analysis of this family of N-EBDC clusters reveals that different terminal ligands affect the fine structures of the cluster cores at different levels. Further studies by cyclic voltammetry indicate that these N-EBDC clusters with distinct terminal ligands exhibit different redox behaviors, furnishing in-depth information on the electronic structure of these clusters potentially related to their reactivity. This study provided useful information for the investigation of nitrogenase related Fe-S clusters toward structural and functional mimicking of the nitrogenase FeMo cofactor.

Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

Syntheses of five types of tungsten-iron-sulfur/selenium clusters, namely, incomplete cubanes, single cubanes, edge-bridged double cubanes (EBDCs), P(N)-type clusters, and double-cuboidal clusters, have been devised using the concept of template-assisted assembly. The template reactant is six-coordinate [(Tp*)W(VI)S(3)](1-) [Tp* = tris(3,5-dimethylpyrazolyl)hydroborate(1-)], which in the assembly systems organizes Fe(2+/3+) and sulfide/selenide into cuboidal [(Tp*)WFe(2)S(3)] or cubane [(Tp*)WFe(3)S(3)Q] (Q = S, Se) units. With appropriate terminal iron ligation, these units are capable of independent existence or may be transformed into higher-nuclearity species. Selenide is used as a surrogate for sulfide in cluster assembly in order to determine by X-ray structures the position occupied by an external chalcogenide nucleophile or an internal chalcogenide atom in the product clusters. Specific incorporation of selenide is demonstrated by the formation of [WFe(3)S(3)Se](2+/3+) cubane cores. Reductive dimerization of the cubane leads to the EBDC core [W(2)Fe(6)S(6)Se(2)](2+) containing μ(4)-Se sites. Reaction of these species with HSe(-) affords the P(N)-type cores [W(2)Fe(6)S(6)Se(3)](1+), in which selenide occupies μ(6)-Se and μ(2)-Se sites. The reaction of [(Tp*)WS(3)](1-), FeCl(2), and Na(2)Se yields the double-cuboidal [W(2)Fe(4)S(6)Se(3)](2+/0) core with μ(2)-Se and μ(4)-Se bridges. It is highly probable that in analogous sulfide-only assembly systems, external and internal sulfide reactants occupy corresponding positions in the cluster products. The results further demonstrate the viability of template-assisted cluster synthesis inasmuch as the reduced (Tp*)WS(3) unit is present in all of the clusters. Structures, zero-field Mössbauer data, and redox potentials are presented for each cluster type.

Cubane-type Co4S4 clusters: synthesis, redox series, and magnetic ground states.

The recent demonstration that the carbene cluster [Fe(4)S(4)(Pr(i)(2)NHCMe(2))(4)] (9) is an accurate structural and electronic analogue of the fully reduced cluster of the iron protein of Azotobacter vinelandii nitrogenase, including a common S = 4 ground state, raises the issue of the existence and magnetism of other [M(4)S(4)L(4)](z) clusters, none of which are known with transition metals other than iron. The system CoCl(2)/Pr(i)(3)P/(Me(3)Si)(2)S/THF assembles [Co(4)S(4)(PPr(i)(3))(4)] (3), which is converted to [Co(4)S(4)(Pr(i)(2)NHCMe(2))(4)] (5) upon reaction with carbene. The clusters support the redox series [3](1-/0/1+) and [5](0/1+/2+); monocations (4, 6) have been isolated by chemical oxidation. Redox potentials and substitution reactions indicate that the carbene is the more effective electron donor to tetrahedral Fe(II) and Co(II) sites. Clusters 3-6 have the same overall cubane-type geometry as 9. Neutral clusters 3 and 5 have an S = 3 ground state. As with the S = 4 state of 9 with local spins S(Fe) = 2, the septet spin state can be described in terms of the coupling of three parallel and one antiparallel spins S(Co) = 3/2. The octanuclear clusters [Co(8)S(8)(PPr(i)(3))(6)](0,1+) were isolated as minor byproducts of the formation and chemical oxidation of 3. The clusters exhibit a rhomb-bridged noncubane (RBNC) structure, whereas clusters with the Fe(8)S(8) core possess edge-bridged double-cubane (EBDC) stereochemistry. There are two structural solutions for the M(8)S(8) core in the form of topological isomers whose stability may depend on valence electron count. A conceptual model for the RBNC <--> EBDC interconversion is presented. (Pr(i)(2)NHCMe(2) = C(11)H(20)N(2) = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene).

Stabilization of Fully Reduced Iron−Sulfur Clusters by Carbene Ligation: The [FenSn]0 Oxidation Levels (n = 4, 8)

The all-ferrous [Fe4S4](0) state has been demonstrated in the fully reduced Fe protein of the Azotobacter vinelandii nitrogenase complex. We seek synthetic analogues of this state more tractable than the recently prepared but highly unstable cluster [Fe4S4(CN)4](4-) (Scott, Berlinguette, Holm, and Zhou, Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 9741). The N-heterocyclic carbene 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (Pr(i)2NHCMe2) has been found to stabilize the fully reduced clusters [Fe8S8(Pr(i)2NHCMe2)6] (4) and [Fe4S4(Pr(i)2NHCMe2)4] (5), which are prepared by cluster assembly or phosphine substitution of FenSn (n = 8, 16) clusters. Cluster 4 is also obtained by reaction of the carbene with all-ferrous [Fe7S6(PEt3)5Cl2] (3) and cluster 5 by carbene cleavage of 4. Detailed structures of 3 (monocapped prismatic), 4, and 5 are described; the latter two are the first iron-sulfur clusters with Fe-C sigma bonds. Cluster 4 possesses the [Fe8(mu3-S) 6(mu4-S)2] edge-bridged double cubane structure and 5 the cubane-type [Fe4(mu3-S)4] stereochemistry. The all-ferrous formulations of the clusters are confirmed by X-ray structure parameters and (57)Fe isomer shifts. Both clusters are stable under conventional aprotic anaerobic conditions, enabling further study of reactivity. The collective properties of 5 indicate that it is a meaningful synthetic analogue of the core of the fully reduced protein-bound cluster.

VFe3S4 Single and Double Cubane Clusters: Synthesis, Structures, and Dependence of Redox Potentials and Electron Distribution on Ligation and Heterometal

Both vanadium and molybdenum cofactor clusters are found in nitrogenase. In biomimetic research, many fewer heterometal MFe3S4 cubane-type clusters have been synthesized with M = V than with M = Mo because of the well-established structural relationship of the latter to the molybdenum coordination unit in the enzyme. In this work, a series of single cubane and edge-bridged double cubane clusters containing the cores [VFe3(mu3-S)4]2+ and [V2Fe6(mu3-S)6(mu4-S)2]2+ have been prepared by ligand substitution of the phosphine clusters [(Tp)VFe3S4(PEt3)3]1+ and [(Tp)2V2Fe6S8(PEt3)4]. The single cubanes [(Tp)VFe3S4L3]2- and double cubanes [(Tp)2V2Fe6S8L4]4- (L= F-, N3-, CN-, PhS-) are shown by X-ray structures to have trigonal symmetry and centrosymmetry, respectively. Single cubanes form the three-member electron transfer series [(Tp)VFe3S4L3]3-,2-,1-. The ligand dependence of redox potentials and electron distribution in cluster cores as sensed by 57Fe isomer shifts (delta) have been determined. Comparison of these results with those previously determined for the analogous molybdenum clusters (Pesavento, Berlinguette, and Holm Inorg. Chem. 2007, 46, 510) allows detection of the influence of heterometal M on the properties. At constant M and variable L, redox potentials are lowest for pi-donor ligands and largest for cyanide and relate approximately with decreasing ferrous character in clusters with constant charge z = 2-. At constant L and z and variable M, EV > E(Mo) and delta(av)V < delta(av)Mo, demonstrating that M = Mo clusters are more readily oxidized and suggesting a qualitative relation between lower potentials (greater ease of oxidation) and ferrous character.

Hydroxide-Promoted Core Conversions of Molybdenum−Iron−Sulfur Edge-Bridged Double Cubanes: Oxygen-Ligated Topological PN Clusters

The occurrence of a heteroatom X (C, N, or O) in the MoFe7S9X core of the iron-molybdenum cofactor of nitrogenase has encouraged synthetic attempts to prepare high-nuclearity M-Fe-S-X clusters containing such atoms. We have previously shown that reaction of the edge-bridged double cubane [(Tp)2Mo2Fe6S8(PEt3)4] (1) with nucleophiles HQ- affords the clusters [(Tp)2Mo2Fe6S8Q(QH)2](3-) (Q = S, Se) in which HQ- is a terminal ligand and Q(2-) is a mu2-bridging atom in the core. Reactions with OH- used as such or oxygen nucleophiles generated in acetonitrile from (Bu3Sn)2O or Me3SnOH and fluoride were examined. Reaction of 1 with Et4NOH in acetonitrile/water generates [(Tp)2Mo2Fe6S9(OH)2]3- (3), isolated as [(Tp)2Mo2Fe6S9(OH)(OC(=NH)Me)(H2O)](3-) and shown to have the [Mo2Fe6(mu2-S)2(mu3-S)6(mu6-S)] core topology very similar to the P(N) cluster of nitrogenase. The reaction system 1/Et4NOH in acetonitrile/methanol yields the P(N)-type cluster [(Tp)2Mo2Fe6S9(OMe)2(H2O)](3-) (5). The system 1/Me3SnOH/F- affords the oxo-bridged double P(N)-type cluster {[(Tp)2Mo2Fe6S9(mu2-O)]2}5- (7), convertible to the oxidized cluster {[(Tp)2Mo2Fe6S9(mu2-O)]2}4- (6), which is prepared independently from [(Tp)2Mo2Fe6S9F2(H2O)](3-)/(Bu3Sn)2O. In the preparations of 3-5 and 7, hydroxide liberates sulfide from 1 leading to the formation of P(N)-type clusters. Unlike reactions with HQ-, no oxygen atoms are integrated into the core structures of the products. However, the half-dimer composition [Mo2Fe6S9O] relates to the MoFe7S9 constitution of the putative native cluster with X = O. (Tp = hydrotris(pyrazolyl) borate(1-)).

Edge-Bridged Mo2Fe6S8 to PN-Type Mo2Fe6S9 Cluster Conversion: Structural Fate of the Attacking Sulfide/Selenide Nucleophile

Reaction of the edge-bridged double cubane cluster [(Tp)(2)M(2)Fe(6)S(8)(PEt(3))(4)] (1; Tp = hydrotris(pyrazolyl)borate(1-)) with hydrosulfide affords the clusters [(Tp)(2)M(2)Fe(6)S(9)(SH)(2)](3)(-)(,4)(-) (M = Mo (2), V), which have been established as the first structural (topological) analogues of the P(N) cluster of nitrogenase. The synthetic reaction is an example of core conversion, resulting in the transformation M(2)Fe(6)(mu(3)-S)(6)(mu(4)-S)(2) (C(i)) --> M(2)Fe(6)(mu(2)-S)(2)(mu(3)-S)(6)(mu(6)-S) (C(2)(v)), the reaction pathway of which is unknown. The most prominent structural feature of P(N)-type clusters is the mu(6)-S atom, which bridges six iron atoms in two MFe(3)S(3) cuboidal halves of the cluster. The initial issue in core conversion is the origin of the mu(6)-S atom. Utilizing SeH(-) as a surrogate reactant for SH(-) in the system 1/SeH(-)/L(-) in acetonitrile, a series of selenide clusters [(Tp)(2)Mo(2)Fe(6)S(8)SeL(2)](3)(-) (L(-) = SH(-) (4), SeH(-) (5), EtS(-) (6), CN(-) (7)) was prepared. The electrospray mass spectra of 4 and 6 revealed inclusion of one Se atom in each cluster, and (1)H NMR spectra and crystallographic refinements of 4-7 indicated that this atom was disordered over the two mu(2)-S/Se positions. The clusters {[(Tp)(2)Mo(2)Fe(6)S(9)](mu(2)-S)}(2)(5)(-) (8) and {[(Tp)(2)Mo(2)Fe(6)S(8)Se](mu(2)-Se)}(2)(5)(-) (9) were prepared from 2 and 5, respectively, and shown to be isostructural. They consist of two P(N)-type cluster units bridged by two mu(2)-S or mu(2)-Se atoms. It is concluded that, in the preparation of 2, the probable structural fate of the attacking nucleophile is as a mu(2)-S atom, and that the mu(3)-S and mu(6)-S atoms of the product cluster derive from precursor cluster 1. Cluster fragmentation during P(N)-type cluster synthesis is unlikely.

Precursors to Clusters with the Topology of the PN Cluster of Nitrogenase: Edge-Bridged Double Cubane Clusters [(Tp)2Mo2Fe6S8L4]z: Synthesis, Structures, and Electron Transfer Series

Members of the cluster set [(Tp)2Mo2Fe6S8L4]z contain the core unit M2Fe6(mu3-S)6(mu4-S)2 in which two MoFe3S4 cubanes are coupled by two Fe-(mu4-S) interactions to form a centrosymmetric edge-bridged double cubane cluster. Some of these clusters are synthetic precursors to [(Tp)2Mo2Fe6S9L2]3-, which possess the same core topology as the P(N) cluster of nitrogenase. In this work, the existence of a three-member electron-transfer series of single cubanes [(Tp)MoFe3S4L3](z) (z = 3-, 2-, 1-) and a four-member series of double cubanes [(Tp)2Mo2Fe6S8L4]z (z = 4-, 3-, 2-, 1-) with L = F-, Cl-, N3, PhS- is demonstrated by electrochemical methods, cluster synthesis, and X-ray structure determinations. The potential of the [4-/3-] couple is extremely low (<-1.5 V vs SCE in acetonitrile) such that the 4- state cannot be maintained in solution under normal anaerobic conditions. The chloride double cubane redox series was examined in detail. The members [(Tp)2Mo2Fe6S8Cl4]4-,3-,2- were isolated and structurally characterized. The redox series includes the reversible steps [4-/3-] and [3-/2-]. Under oxidizing conditions, [(Tp)2Mo2Fe6S8Cl4]2- cleaves with the formation of single cubane [(Tp)MoFe3S4Cl3]1-. The quasireversible [2-/1-] couple is observed at more positive potentials than those of the single cubane redox step. Structure comparison of nine double cubanes suggests that significant dimensional changes pursuant to redox reactions are mainly confined to the Fe2(mu4-S)2 bridge rhomb. The synthesis and structure of [(Tp)2Mo2Fe6S9F2.H2O]3-, a new topological analogue of the P(N) cluster of nitrogenase, is described. (Tp = hydrotris(pyrazolyl)borate(1-)).

Heterometal cubane-type WFe 3S 4 and related clusters trigonally symmetrized with hydrotris(3,5-dimethylpyrazolyl)borate

The scope of formation and structures of tungsten–iron–sulfur clusters has been explored using reactions based on [(Tp*)WS 3] 1− ( 1) as the ultimate precursor. The reaction system 1/FeCl 2/NaSEt/S affords the cubane cluster [(Tp*)WFe 3S 4Cl 3] 1− ( 2), which with NaSEt is converted to [(Tp*)WFe 3S 4(SEt) 3] 1− ( 3).Clusters 2 and 3 contain the cubane [WFe 3(μ 3-S) 4] 3+ core.Complex 1 with FeCl 2/NaSEt forms [(Tp*)WFe 2S 3Cl 2(SEt)] 1− ( 4) with the cuboidal [WFe 2(μ 2-S) 2(μ 3-S)(μ 2-SR)] 2+ core.Treatment of 2 with excess Et 3P yields the edge-bridged double [(Tp*) 2W 2Fe 6S 8(PEt 3) 4] ( 5) with the [W 2Fe 6(μ 3-S) 6(μ 4-S) 2] core. Reaction of 2 with excess Et 3 P / BH 4 - / HS - leads a mixture of products, from which [(Tp*) 2W 2Fe 5S 9Na(SH)(MeCN)] 3−( 6) was identified.This cluster, as closely related [(Tp) 2Mo 2Fe 6S 9(SH) 2] 3−, exhibits a core topology [W 2Fe 5Na(μ 2-S) 2(μ 3-S) 6(μ 6-S)] very similar to the P N cluster of nitrogenase. All reactions were carried out in acetonitrile. The structures of 2– 6 were established crystallographically as Et 4N + salts. In the cubane series, substitution of tungsten for molybdenum decreases the [MFe 3S 4] 3+/2+ redox potential by ca. 0.20 V but has a negligible effect on electron distribution. This work expands the small set of previously known weak-field W–Fe–S clusters, demonstrates the existence of tungsten-containing edge-bridged double cubanes and clusters with the P N core topology, and introduces a new cuboidal core structure as found in 4 (Tp = hydrotris(pyrazolyl)borate, Tp* = hydrotris(3,5-dimethylpyrazolyl)borate).

Structural conversions of molybdenum-iron-sulfur edge-bridged double cubanes and P(n)-type clusters topologically related to the nitrogenase P-cluster.

Edge-bridged Mo-Fe-S double cubanes are versatile precursors for the synthesis of other clusters of the same nuclearity. Thus, the double cubane [(Tp)(2)Mo(2)Fe(6)S(8)(PEt(3))(4)] sustains terminal ligand substitution with retention of the Mo(2)Fe(6)(micro(3)-S)(6)(micro(4)-S)(2) core structure and rearrangement to the Mo(2)Fe(6)(micro(2)-S)(2)(micro(3)-S)(6)(micro(6)-S) topology of the nitrogenase P(N) cluster upon reaction with certain nucleophiles. Four distinct processes for the conversion of double cubanes to P(N)-type clusters are documented, affording the products [(Tp)(2)Mo(2)Fe(6)S(9)(SR)(2)](3)(-), [(Tp)(2)Mo(2)Fe(6)S(8)(OMe)(3)](3)(-), and [(Tp)(2)Mo(2)Fe(6)S(7)(OMe)(4)](2)(-). In the latter clusters, two methoxides are terminal ligands and one or two are micro(2)-bridging ligands. The reverse transformation of a P(N)-type cluster to an edge-bridged double cubane has been demonstrated by the reaction of [(Tp)(2)Mo(2)Fe(6)S(8)(OMe)(3)](3)(-) with Me(3)SiX to afford [(Tp)(2)Mo(2)Fe(6)S(8)X(4)](2)(-) (X = Cl(-), Br(-)). Edge-bridged double cubanes have been obtained in the oxidation states [Mo(2)Fe(6)S(8)](2+,3+,4+). The stable oxidation state of P(N)-type clusters is [Mo(2)Fe(6)S(9)](+). Structures of five double cubanes and four P(N)-type clusters are reported. The P(N)-type clusters are synthetic representations of the biologically unique topology of the native P(N) cluster. Best-fit superpositions of the native and synthetic cluster cores gives weighted rms deviations in atom positions of 0.20-0.38 A. This study and an earlier investigation (Zhang, Y.; Holm, R. H. J. Am. Chem. Soc. 2003, 125, 3910-3920) provide a comprehensive account of the synthesis of structural analogues of the native P(N) cluster and provide the basis for continuing investigation of the synthesis of weak-field Mo-Fe-S clusters related to nitrogenase. (Tp = tris(pyrazolyl)hydroborate(1-).)

Vanadium-iron-sulfur clusters containing the cubane-type [VFe3S4] core unit: synthesis of a cluster with the topology of the PN cluster of nitrogenase.

A synthetic method affording a topological analogue of the electron-transfer P-cluster of nitrogenase (Fe(8)S(7)(mu(2)-S(Cys))(2)) in the P(N) state has been devised, based in part on our previous development of cubane-type VFe(3)S(4) clusters (Hauser, C.; Bill, E.; Holm, R. H. Inorg. Chem. 2002, 41, 1615-1624). The cluster [(Tp)VFe(3)S(4)Cl(3)](2-) (1) is converted to [(Tp)VFe(3)S(4)(PR(3))(3)](1+) (R = Et (2), Bu (3)) by reaction with R(3)P. The phosphine ligands are readily substituted, leading to [(Tp)VFe(3)S(4)(SR)(3)](2-) (R = Ph (4), H (5)). Reduction of 2 or 3 with cobaltocene produces the edge-bridged double cubanes [(Tp)(2)V(2)Fe(6)S(8)(PR(3))(4)] (R = Et (6), Bu (7)), which are readily converted to [(Tp)(2)V(2)Fe(6)S(8)(SPh)(4)](4-) (8). The structures of clusters 3-5 and 8 were proven crystallographically. Cluster 8 has the double-cubane structure previously shown for 6, in which two cubane units are bridged by two Fe-(mu(4)-S) bonds. (57)Fe isomer shifts are consistent with the formulation [VFe(2.33+)(3)S(4)](2+) for the single cubanes and the all-ferrous description 2[VFe(2+)(3)S(4)](1+) for the double cubanes. Reaction of 6 with 4 equiv of (Et(4)N)(HS) in acetonitrile results in the insertion of sulfide with concomitant structural rearrangement and the formation of [(Tp)(2)V(2)Fe(6)S(9)(SH)(2)](4-) (10), obtained in ca. 50% yield as the Et(4)N(+) salt. The cluster has C(2) symmetry, with two all-ferrous VFe(3)S(4) fragments bridged by a common mu(6)-S atom and two mu(2)-S atoms that simulate the bridging atoms in the two Fe-(mu(2)-S(Cys))-Fe bridges of the P(N) cluster. The bridge pattern V(2)Fe(6)(mu(2)-S)(2)(mu(3)-S)(6)(mu(6)-S) and cluster shape match those of the native cluster. A best-fit superposition of the cores of 10 and the P(N) cluster affords a weighted rms deviation in atom positions of 0.33 A. Cluster 10 and [(Tp)(2)Mo(2)Fe(6)S(9)(SH)(2)](3-), prepared by a related route (Zhang, Y.; Holm, R. H. J. Am. Chem. Soc. 2003, 125, 3910-3920), demonstrate that the topology of the P(N) cluster can be achieved in molecular form in the absence of protein structure (Tp = tris(pyrazolyl)hydroborate).

Synthesis and reactions of cubane-type iron-sulfur-phosphine clusters, including soluble clusters of nuclearities 8 and 16.

A family of soluble, reduced iron-sulfur clusters with nuclearities 4, 8, and 16 having tertiary phosphine ligation and based on the Fe(4)S(4) cubane-type structural motif has been synthesized. The results of this investigation substantially extend and improve the results of our original work on iron-sulfur-phosphine clusters (Goh, C.; Segal, B. M.; Huang, J.; Long, J. R.; Holm, R. H. J. Am. Chem. Soc. 1996, 118, 11844). A general property of this cluster family is facile phosphine substitution. The clusters [Fe(4)S(4)(PR(3))(4)](+) are precursors to monosubstituted [Fe(4)S(4)(PR(3))(3)X] (X = Cl-, RS-), homoleptic [Fe(4)S(4)(SR)(4)](3-), and all-ferrous monocubanes [Fe(4)S(4)(PR(3))(4)] (R = Pr(i), Cy, Bu(t); generated in solution). In turn, [Fe(4)S(4)(PPr(i)()(3))(3)(SSiPh(3))] and [Fe(4)S(4)(PPr(i)(3))(4)] can be transformed into the dicubanes [Fe(8)S(8)(PPr(i)()(3))(4)(SSiPh(3))(2)] and [Fe(8)S(8)(PPr(i)((3))(6)], respectively. Further, the tetracubanes [Fe(16)S(16)(PR(3))(8)] are also accessible from [Fe(4)S(4)(PR(3))(4)] under different conditions. X-ray structures are described for [Fe(4)S(4)(PCy(3))(3)X] (X = Cl-, PhS-), [Fe(8)S(8)(PPr(i)(3))(4)(SSiPh(3))(2)], [Fe(8)S(8)(PPr(i)()(3))(6)], and [Fe(16)S(16)(PCy(3))(8)]. The monosubstituted clusters show different distortions of the [Fe(4)S(4)](+) cores from idealized cubic symmetry. The dicubanes possess edge-bridged double cubane structures with an Fe(2)(mu(4)-S)(2) bridge rhomb and idealized C(2)(h)() symmetry. The ready cleavage of these clusters into single cubanes is considered a probable consequence of strained bond angles at the mu(4)-S atoms. Tetracubanes contain four individual cubanes, each of which is implicated in two bridge rhombs so as to generate a cyclic structure of idealized D(4) symmetry. Redox properties and Mössbauer spectroscopic parameters are reported. The species [Fe(4)S(4)(PR(3))(4)] (in solution), [Fe(8)S(8)(PR(3))(6)], and [Fe(16)S(16)(PR(3))(8)] are the only synthetic all-ferrous clusters with tetrahedral iron sites that have been isolated. Their utility as precursors to other highly reduced iron-sulfur clusters is under investigation.

Rearrangement of symmetrical dicubane clusters into topological analogues of the P cluster of nitrogenase: nature's choice?

Reaction schemes have been developed that lead to clusters having the topology of the PN cluster of nitrogenase. The single cubane clusters [(Tp)MFe3S4Cl3]z (M = Mo, z = 1-; M = V, z = 2-) react with PEt3 to give [(Tp)MFe3S4(PEt3)3]1+, which are reduced to the neutral edge-bridged double cubanes [(Tp)2M2Fe6S8(PEt3)4] with highly reduced (2[MFe3S4]1+) cores. Reaction of these clusters in acetonitrile with (Et4N)(HS) results in the formation of [(Tp)2Mo2Fe6S9(SH)2]3- and [(Tp)2V2Fe6S9(SH)2]4-. X-ray structures of the Et4N+ salts reveal the bridging pattern M2Fe6(mu2-S)2(mu3-S)6(mu6-S) in which two cuboidal MFe3(mu3-S)3 units share the common bridge atom mu6-S and are externally bridged by two mu2-S atoms. The M sites possess trigonal octahedral, and the Fe sites, distorted tetrahedral coordination. Hydrosulfide ligands and sulfide atoms simulate terminal cysteinate ligation and mu2 bridges, respectively, in the protein-bound cluster Fe8S7(mu2-SCys)2(SCys)4. The synthetic clusters have the same bridging pattern as the PN cluster and approach congruency with it. These clusters are the first molecular topological analogues of a PN cluster. Like the latter, they are substantially reduced (majority of Fe(II)).

Molybdenum−Iron−Sulfur Clusters of Nuclearities Eight and Sixteen, Including a Topological Analogue of the P-Cluster of Nitrogenase

Transformations of the edge-bridged double cubane cluster [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4] (1) under reducing conditions have been investigated as synthetic approaches to the clusters of nitrogenase. Cluster 1 is a versatile precursor to different Mo-Fe-S cluster types. The reaction system 1/K(C14H10) in THF yields the reduced cluster [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4]1- (2), which as its crystalline Et4N+ salt retains the edge-bridged structure of 1. X-ray structural and Mössbauer spectroscopic results indicate an unsymmetrical electron distribution with localized [MoFe3S4]2+,1+ cubane-type units. The system 1/2K(C14H10)/2HS- in THF/acetonitrile affords [(Cl4cat)4(Et3P)4Mo4Fe12S20K3(DMF)]5- (3), whose structure was determined as the Ph3PMe+ salt. The cluster consists of two isostructural Mo2Fe6S9 fragments connected by two mu 2-S bridges. Three potassium ions are bound between the two fragments. In each fragment, the iron atoms are present in tetrahedral FeS4 and the molybdenum atoms in octahedral MoO2PS3 coordination units, and two MoFe3(mu 3-S)3 cuboidal units are bridged by a common mu 6-S atom. The fragments have idealized mirror symmetry and are isostructural with two of the fragments present in the previously reported high-nuclearity cluster [(Cl4cat)6(Et3P)6Mo6Fe20S30]8- (4) (Osterloh, F.; Sanakis, Y.; Staples, R. J.; Münck, E.; Holm, R. H. Angew. Chem., Int. Ed. Engl. 1999, 38, 2066). On the basis of overall shape, atom connectivities, and metric features, the Mo2Fe6S9 fragment is a topological analogue of the P-cluster of nitrogenase in the PN (reduced) state. A third cluster type, formed as a minor byproduct in the reaction system leading to 2, was crystallographically identified as [(Cl4cat)2(Et3P)2Mo2Fe6S8(PEt3)4]4-, whose core is made up of two MoFe3(mu 3-S)3 cuboidal units bridged by two mu 2-S atoms and connected by a direct Fe-Fe bond. Full structural details and the redox properties of 2 and 3 are reported.