Terminal Hydride Ligands Research Articles

Low-Coordinate Iron Hydride Chemistry at an N,N,C-Heteroscorpionate Platform.

Locally high-spin iron hydrides are proposed to play a critical role as intermediates in iron-molybdenum cofactor (FeMoco)-catalyzed N2 fixation. Inspired by these biological systems, we report herein our initial investigations into low-coordinate iron hydride chemistry supported by our N,N,C-heteroscorpionate ligands. Those ligands with smaller steric profiles are unable to completely suppress the formation of a binuclear [Fe(μ2-H)]2 complex; however, the incorporation of more substantial steric bulk allows for the isolation of a rare example of a terminal, high-spin (S = 2) Fe2+ hydride. Fourier transform infrared spectroscopy suggests an unusually weak Fe-H bond in the latter molecule. Mössbauer spectroscopies, coupled with density functional theory calculations, highlights the substantial influence of the terminal hydride ligand on 57Fe isomer shift.

Undirected C-H Bond Activation in Aluminium Hydrido Enaminonates.

Two new aluminium hydrido complexes were synthesized by reacting AlH3 with the enaminone ligand N-(4,4,4-trifluorobut-1-en-3-on)-6,6,6-trifluoroethylamine (HTFB-TFEA) in different molar ratios to obtain mono- and di-hydrido-aluminium enaminonates. Both air and moisture sensitive compounds could be purified via sublimation under reduced pressure. The spectroscopic analysis and structural motif of the monohydrido compound [H-Al(TFB-TBA)2] (3) showed a monomeric 5-coordinated Al(III) centre bearing two chelating enaminone units and a terminal hydride ligand. However, the dihydrido compound exhibited a rapid C-H bond activation and C-C bond formation in the resulting compound [(Al-TFB-TBA)-HCH2] (4a), which was confirmed by single crystal structural data. The intramolecular hydride shift involving the migration of a hydride ligand from aluminium centre to the alkenyl carbon of the enaminone ligand was probed and verified by multi-nuclear spectral studies (1H,1H NOESY, 13C, 19F, and 27Al NMR).

Structural characterization of three hydride-bridged sodium aluminate compounds

The synthesis and single-crystal structures of three hydride-bridged sodium aluminate compounds containing the utility amide HMDS [N(SiMe3)2 or C6H18NSi2] are reported. Both bis[bis(trimethylsilyl)amido-2κN]-μ-hydrido-hydrido-2κH-(N,N,N′,N′′,N′′-pentamethyldiethylenetriamine-1κ3 N,N′,N′′)(tetrahydrofuran-1κO)aluminiumsodium, [AlNa(C6H18NSi2)2H2(C4H8O)(C9H23N3)] or (HMDS)2Al(H)2Na(THF)(PMDETA), (1) (THF = tetrahydrofuran, C4H8O; PMDETA = N,N,N′,N′′,N′′-pentamethyldiethylenetriamine, C9H23N3) and tetrakis[bis(trimethylsilyl)amido]-3κ2 N,4κ2 N-tetra-μ-hydrido-tetrakis(tetrahydrofuran)-1κ2 O,2κ2 O-dialuminiumdisodium, [Al2Na2(C6H18NSi2)4H4(C4H8O)4] or [(HMDS)2Al(H)2Na(THF)2]2 (2), are dihydrides. However, 1 is a dinuclear Al—H—Na monomer with one bridging and one terminal hydride ligand whilst in 2 all the hydride ligands bridge between Al and Na atoms to give a dimeric structure with a core (AlHNaH)2 eight-membered ring. In contrast, the structure of bis[bis(trimethylsilyl)amido]-3κN,4κN-dihydrido-3κH,4κH-tetra-μ-hydrido-bis(N,N,N′,N′′,N′′-pentamethyldiethylenetriamine)-1κ3 N,N′,N′′;2κ3 N,N′,N′′-dialuminiumdisodium, [Al2Na2(C6H18NSi2)2H6(C9H23N3)2] or [(HMDS)Al(H)3Na(PMDETA)]2 (3), also contains a (AlHNaH)2 eight-membered ring but is a trihydride with two bridging and one terminal hydride ligand per Al centre. The (AlHNaH)2 eight-membered rings of 2 and 3 differ in their structural details. That of 2 is based around a twofold axis and has a larger Al...Al intra-ring distance than that found in centrosymmetric 3.

Kinetic stabilization of low-oxidation state and terminal hydrido main group metal complexes by a sterically demanding N,N'-bis(2,6-terphenyl)triazenide.

A sterically demanding N,N'-bis(2,6-terphenyl)triazenide was employed to stabilize a number of low-coordinate main group metal terminal hydride complexes. These complexes display enhanced thermal stabilities relative to analogous complexes ligated by β-diketiminates, which we attribute to the steric shielding of the metal hydride moiety by the ligand. We also show this triazenide ligand can stabilize low-oxidation state Group 13 metals. DFT calculations conducted on these triazenide ligated Group 13 metal(i) complexes revealed they possess a narrower HOMO-LUMO gap relative to analogous complexes ligated by other monoanionic N,N'-ligands. In addition, several heteroleptic Group 13 metal(iii) and Group 14 metal(ii) complexes featuring this triazenide are reported.

Reactivity toward Unsaturated Small Molecules of Thiolate-Bridged Diiron Hydride Complexes.

In the presence of 1 equiv of tBuNC, the homolytic cleavage of the FeIII-H bond in the diiron terminal hydride complex [Cp*Fe( t-H)(μ-η2:η4-bdt)FeCp*][BF4] (1[BF4]) smoothly took place to release 1/2 H2, followed by binding of a tBuNC group to the unsaturated FeII center. Interestingly, upon exposure of 1[BF4] to 1 atm of acetylene, the isomerization process of the hydride ligand from the terminal to bridging coordination site was unaffected. Upon treatment of the diiron hydride bridged complex 2[BF4] with acetylene at 30 °C, two FeIII-H bonds were broken, and then an acetylene molecule was coordinated to the diiron centers in a novel μ-η2:η2 side-on fashion. In the above reaction system, the hydride ligands whether terminal or bridging all play a role as the electron donor for the reduction of the diiron centers from FeIIIFeIII to FeIIIFeII. These reaction patterns are reminiscent of the vital E4 state responsible for N2 binding and H2 liberation in the catalytic cycle of nitrogenase, which contains two {Fe-H-Fe} motifs as electron reservoirs for the reduction of the iron centers. Differently, when treating 1[BF4] with TMSN3, the terminal hydride ligand was inserted into the azide group to give a diiron amide complex 4[BF4] in moderate yield.

Synthesis, Structure, and Reactivity of a Terminal Magnesium Hydride Compound with a Carbatrane Motif, [TismPriBenz]MgH: A Multifunctional Catalyst for Hydrosilylation and Hydroboration.

The tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl)]methyl ligand, [TismPriBenz], has been employed to form the magnesium carbatrane compound, [TismPriBenz]MgH, which possesses a terminal hydride ligand. Specifically, [TismPriBenz]MgH is obtained via the reaction of [TismPriBenz]MgMe with PhSiH3. The reactivity of [TismPriBenz]MgMe and [TismPriBenz]MgH allows access to a variety of other structurally characterized carbatrane derivatives, including [TismPriBenz]MgX [X = F, Cl, Br, I, SH, N(H)Ph, CH(Me)Ph, O2CMe, S2CMe]. In addition, [TismPriBenz]MgH is a catalyst for (i) hydrosilylation and hydroboration of styrene to afford the Markovnikov products, Ph(Me)C(H)SiH2Ph and Ph(Me)C(H)Bpin, and (ii) hydroboration of carbodiimides and pyridine to form N-boryl formamidines and N-boryl 1,4- and 1,2-dihydropyridines, respectively.

Interplay between Terminal and Bridging Diiron Hydrides in Neutral and Oxidized States.

This study describes the structural, spectroscopic, and electrochemical properties of electronically unsymmetrical diiron hydrides. The terminal hydride Cp*Fe(pdt)Fe(dppe)(CO)H ([1(t-H)]0, Cp*- = Me5C5-, pdt2- = CH2(CH2S-)2, dppe = Ph2PC2H4PPh2) was prepared by hydride reduction of [Cp*Fe(pdt)Fe(dppe)(CO)(NCMe)]+. As established by X-ray crystallography, [1(t-H)]0 features a terminal hydride ligand. Unlike previous examples of terminal diiron hydrides, [1(t-H)]0 does not isomerize to the bridging hydride [1(μ-H)]0. Oxidation of [1(t-H)]0 gives [1(t-H)]+, which was also characterized crystallographically as its BF4- salt. Density functional theory (DFT) calculations indicate that [1(t-H)]+ is best described as containing an Cp*FeIII center. In solution, [1(t-H)]+ isomerizes to [1(μ-H)]+, as anticipated by DFT. Reduction of [1(μ-H)]+ by Cp2Co afforded the diferrous bridging hydride [1(μ-H)]0. Electrochemical measurements and DFT calculations indicate that the couples [1(t-H)]+/0 and [1(μ-H)]+/0 differ by 210 mV. Qualitative measurements indicate that [1(t-H)]0 and [1(μ-H)]0 are close in free energy. Protonation of [1(t-H)]0 in MeCN solution affords H2 even with weak acids via hydride transfer. In contrast, protonation of [1(μ-H)]0 yields 0.5 equiv of H2 by a proposed protonation-induced electron transfer process. Isotopic labeling indicates that μ-H/D ligands are inert.

Binuclear cyclopentadienylrhenium hydride chemistry: terminal versus bridging hydride and cyclopentadienyl ligands.

Theoretical studies predict the lowest energy structures of the binuclear cyclopentadienylrhenium hydrides Cp2Re2H n (Cp = η(5)-C5H5; n = 4, 6, 8) to have a central doubly bridged Re2(μ-H)2 unit with terminal η(5)-Cp rings and the remaining hydrides as terminal ligands. However, the lowest energy Cp2Re2H2 structure by more than 12 kcal mol(-1) has one terminal η(5)-Cp ring, a bridging η(3),η(2)-Cp ring, and two terminal hydride ligands bonded to the same Re atom. The lowest energy hydride-free Cp2Re2 structure is a perpendicular structure with two bridging η(3),η(2)-Cp rings. The previously predicted bent singlet Cp2Re2 structure with terminal η(5)-Cp rings and a formal Re-Re sextuple bond lies ∼37 kcal mol(-1) above this lowest energy (η(3),η(2)-Cp)2Re2 structure. The thermochemistry of the CpReH n and Cp2Re2H n systems is consistent with the reported synthesis of the permethylated derivatives Cp*ReH6 and Cp*2Re2H6 (Cp* = η(5)-Me5C5) as very stable compounds. Additionally, natural bond orbital analysis, atoms-in-molecules and overlap population density-of-state in AOMIX were applied to present the existence of rhenium-rhenium multiple bonds.

The formation of a σ-bond complex vs. an oxidation addition product in reaction of [M(CO)4(η4-nbd)] (M = W, Mo) and H–EEt3 (E = Si, Ge, Sn): DFT optimized structures and predicted chemical shifts of hydride ligands

Density functional theory calculations have been employed to understand the bonding and structural features of the key intermediate complexes formed during the catalytic cycle for the hydrogermylation, hydrosilylation and hydrostannation of norbornadiene (nbd) in the photochemical reaction of the tungsten(0) and molybdenum(0) carbonyl complex [M(CO)4(η4-nbd)] (M = Mo, W) and H–EEt3 (E = Si, Ge, Sn). The structure of the σ-bond complexes [M(CO)3(η2-H–EEt3)(η4-nbd)] (1) and the seven-coordinate hydride complexes [MH(EEt3)(CO)3(η4-nbd)] (2) have been optimized. The calculated values of the chemical shift for the σ-bond proton in complex 1 and the terminal hydride ligand in the oxidative addition product complex 2 have been compared with recently published experimental data for complexes of this type.

New Reactions of Terminal Hydrides on a Diiron Dithiolate

Mechanisms for biological and bioinspired dihydrogen activation and production often invoke the intermediacy of diiron dithiolato dihydrides. The first example of such a Fe2(SR)2H2 species is provided by the complex [(term-H)(μ-H)Fe2(pdt)(CO)(dppv)2] ([H1H](0)). Spectroscopic and computational studies indicate that [H1H](0) contains both a bridging hydride and a terminal hydride, which, notably, occupies a basal site. The synthesis begins with [(μ-H)Fe2(pdt)(CO)2(dppv)2](+) ([H1(CO)](+)), which undergoes substitution to afford [(μ-H)Fe2(pdt)(CO)(NCMe)(dppv)2](+) ([H1(NCMe)](+)). Upon treatment of [H1(NCMe)](+) with borohydride salts, the MeCN ligand is displaced to afford [H1H](0). DNMR (EXSY, SST) experiments on this complex show that the terminal and bridging hydride ligands interchange intramolecularly at a rate of 1 s(-1) at -40 °C. The compound reacts with D2 to afford [D1D](0), but not mixed isotopomers such as [H1D](0). The dihydride undergoes oxidation with Fc(+) under CO to give [1(CO)](+) and H2. Protonation in MeCN solution gives [H1(NCMe)](+) and H2. Carbonylation converts [H1H](0) into [1(CO)](0).

Bimetallic osmium-tin complexes: Stannylene and hydrostannylene clusters upon addition of Ph3SnH to unsaturated triosmium clusters [(μ-H)2Os3(CO)8(μ-diphosphine)] (diphosphine = dppm, dppf)

Products of the addition of Ph3SnH to the unsaturated triosmium clusters [(μ-H)2Os3(CO)8(μ-dppm)] (1) and [(μ-H)2Os3(CO)8(μ-dppf)] (2) are highly dependent on the nature of the diphosphine. With the rigid bis(diphenylphosphino)methane (dppm), the stannylene complex [H2Os3(CO)7(μ-SnPh2)2(μ-dppm)] (3) is the major cluster product (35% yield), resulting from both Sn–H and Sn–C bond activation, while two previously reported triphenyltin complexes, [(μ-H)2Os3(CO)8(SnPh3)2(μ-dppm)] (4) (10% yield) and [(μ-H)2Os3(CO)8(SnPh3){μ-Ph2PCH2P(Ph)C6H4}] (5) (11% yield) also result. Biphenyl is also a co-product of this reaction and it is postulated to be formed concomitantly with 3. A similar reaction with the highly flexible 1,1′-bis(diphenylphosphino)ferrocene (dppf) complex leads to the formation of four tin-containing complexes: two previously reported compounds [HOs(CO)4(SnPh3)] (6) (8% yield) and [Os2(CO)6(SnPh3)2(μ-SnPh2)2] (8) (5% yield), and the new triphenyltin and hydrostannylene clusters [H(μ-H)2Os3(CO)8(SnPh3)(μ-dppf)] (10) (22% yield) and [(μ-H)Os2(CO)4(SnPh3)2(μ-HSnPh2)(μ-dppf)] (9) (12% yield) respectively, together with the dihydroxy cluster [Os3(CO)8(μ-OH)2(μ-dppf)] (7). Two of these new clusters have been characterized by X-ray crystallography. Cluster 3 consists of a central Os3 triangle with two stannylene groups, each bridging one Os–Os edge, a dppm ligand that bridges the third Os-Os edge, and two terminal hydride ligands. Cluster 10 consists of an Os3 triangle with a terminal SnPh3 group, one terminal and two bridging hydride ligands, and a bridging dppf ligand. The new compounds 3, 7, 9, and 10 have been investigated by electronic structure calculations, and the computed ground-state structures are discussed relative to the X-ray crystallographic structures.

Binuclear rare-earth polyhydride complexes bearing both terminal and bridging hydride ligands

The first binuclear rare-earth tetrahydride complexes [(NCN)LnH2]2(THF)3 (1-Ln; LnY, Lu; NCNPhC(NC6H3iPr2-2,6)2) bearing both terminal and bridging hydride ligands were obtained by hydrogenolysis of the dialkyl precursors. These novel binuclear hydride complexes underwent unique Ln-H addition reactions with various unsaturated compounds such as 2,6-dimethylphenyl isocyanide, diphenylacetylene and 1,4-diphenyl-1,3-butadiyne.

Facile Activation of Dihydrogen by a Phosphinito-Bridged Pt(I)−Pt(I) Complex

The phosphinito-bridged Pt(I) complex [(PHCy(2))Pt(mu-PCy(2)){kappa(2)P,O-mu-P(O)Cy(2)}Pt(PHCy(2))](Pt-Pt) (1) reversibly adds H(2) under ambient conditions, giving cis-[(H)(PHCy(2))Pt(1)(mu-PCy(2))(mu-H)Pt(2)(PHCy(2)){kappaP-P(O)Cy(2)}](Pt-Pt) (2). Complex 2 slowly isomerizes spontaneously into the corresponding more stable isomer trans-[(PHCy(2))(H)Pt(mu-PCy(2))(mu-H)Pt(PHCy(2)){kappaP-P(O)Cy(2)}](Pt-Pt) (3). DFT calculations indicate that the reaction of 1 with H(2) occurs through an initial heterolytic splitting of the H(2) molecule assisted by the phosphinito oxygen with breaking of the Pt-O bond and hydrogenation of the Pt and O atoms, leading to the formation of the intermediate [(PHCy(2))(H)Pt(mu-PCy(2))Pt(PHCy(2)){kappaP-P(OH)Cy(2)}](Pt-Pt) (D), where the two split hydrogen atoms interact within a six-membered Pt-H...H-O-P-Pt ring. Compound D is a labile intermediate which easily evolves into the final dihydride complex 2 through a facile (9-15 kcal mol(-1), depending on the solvent) hydrogen shift from the phosphinito oxygen to the Pt-Pt bond. Information obtained by addition of para-H(2) on 1 are in agreement with the presence of a heterolytic pathway in the 1 --> 2 transformation. NMR experiments and DFT calculations also gave evidence for the nonclassical dihydrogen complex [(PHCy(2))(eta(2)-H(2))Pt(mu-PCy(2))Pt(PHCy(2)){kappaP-P(O)Cy(2)}](Pt-Pt) (4), which is an intermediate in the dehydrogenation of 2 to 1 and is also involved in intramolecular and intermolecular exchange processes. Experimental and DFT studies showed that the isomerization 2 --> 3 occurs via an intramolecular mechanism essentially consisting of the opening of the Pt-Pt bond and of the hydrogen bridge followed by the rotation of the coordination plane of the Pt center with the terminal hydride ligand.

Influence of the [2Fe]H Subcluster Environment on the Properties of Key Intermediates in the Catalytic Cycle of [FeFe] Hydrogenases: Hints for the Rational Design of Synthetic Catalysts

Nature's recipe: A theoretical study analyzes how the environment of the [FeFe] hydrogenase's catalytic cofactor affects its chemical properties, particularly the relative stability of complexes with bridging and terminal hydride ligands (see picture; Fe teal, S yellow, C green, N blue, O red, H gray). The results help to elucidate key rules for the design of bioinspired synthetic catalysts for H(2) production.

Addition of Ammonia, Water, and Dihydrogen Across a Single Pd−Pd Bond

Pincer-supported Pd alkyl complexes (PNP)PdR undergo photochemical conversion to a dimeric (PNP)Pd−Pd(PNP) complex with a single Pd−Pd bond. Dissociation of the dimer into monomeric (PNP)Pd species is kinetically accessible thermally and photochemically. (PNP)Pd−Pd(PNP) reacts with ammonia, water, and dihydrogen by adding the H−X bond of the substrate (X = NH2, OH, H) across the Pd−Pd bond. For ammonia, this represents a rare example of conversion of NH3 to terminal hydride and amide ligands by a bimetallic complex.

Di-μ-benzenethiolato-μ-chlorido-bis{hydrido[(S)-(−)-2,2′-bis(di-p-tolylphosphanyl)-1,1′-binaphthyl]iridium(III)} chloride 1,2-dichloroethane disolvate

The cation of the title compound, [Ir2ClH2(C6H5S)2(C48H40P2)2]Cl·2C2H4Cl2, exists as a bridged bifacial octahedral dinuclear iridium structure with C 2 symmetry (Cl lies on the rotation axis). The coordination environment of the Ir atom can be described as highly distorted octahedral with two P atoms, two bridging phenyl thiolato S atoms, a bridging chloride ligand, and a terminal hydride ligand.

Zeolite-Encaged Iridium Clusters with Hydride Ligands: Characterization by Extended X-Ray Absorption Fine Structure, NMR, and Inelastic Neutron Scattering Vibrational Spectroscopies

A family of NaY zeolite-supported iridium clusters was prepared by reductive carbonylation of Ir(CO)2(acac) sorbed in the zeolite pores to form Ir6(CO)16, which was decarbonylated by treatment in He. This method allowed preparation of samples with Ir contents as high as 33.0 wt.%. Extended X-ray absorption fine structure spectra of the decarbonylated samples indicate that the clusters are well approximated as octahedral Ir6 in the zeolite cages. The high loadings of clusters in the zeolite allowed characterization of the hydride ligands on the clusters by 1H NMR spectroscopy and inelastic neutron scattering spectroscopy. These ligands exist on the clusters even in the absence of H2 in the gas phase, presumably equilibrated with OH groups on the zeolite. The data indicate both terminal and bridging hydride ligands on the clusters. The H/Ir atomic ratio is estimated to be approximately 0.01 on the basis of the 1H NMR data and thermogravimetric analysis of the sample.

M−P versus MM Bonds as Protonation Sites in the Organophosphide-Bridged Complexes [M2Cp2(μ-PR2)(μ-PR‘2)(CO)2], (M = Mo, W; R, R‘ = Ph, Et, Cy)

The unsaturated complexes [W2Cp2(mu-PR2)(mu-PR'2)(CO)2] (Cp = eta5-C5H5; R = R' = Ph, Et; R = Et, R' = Ph) react with HBF4.OEt2 at 243 K in dichloromethane solution to give the corresponding complexes [W2Cp2(H)(mu-PR2)(mu-PR'2)(CO)2]BF4, which contain a terminal hydride ligand. The latter rearrange at room temperature to give [W2Cp2(mu-H)(mu-PR2)(mu-PR'2)(CO)2]BF4, which display a bridging hydride and carbonyl ligands arranged parallel to each other (W-W = 2.7589(8) A when R = R' = Ph). This explains why the removal of a proton from the latter gives first the unstable isomer cis-[W2Cp2(mu-PPh2)2(CO)2]. The molybdenum complex [Mo2Cp2(mu-PPh2)2(CO)2] behaves similarly, and thus the thermally unstable new complexes [Mo2Cp2(H)(mu-PPh2)2(CO)2]BF4 and cis-[Mo2Cp2(mu-PPh2)2(CO)2] could be characterized. In contrast, related dimolybdenum complexes having electron-rich phosphide ligands behave differently. Thus, the complexes [Mo2Cp2(mu-PR2)2(CO)2] (R = Cy, Et) react with HBF4.OEt2 to give first the agostic type phosphine-bridged complexes [Mo2Cp2(mu-PR2)(mu-kappa2-HPR2)(CO)2]BF4 (Mo-Mo = 2.748(4) A for R = Cy). These complexes experience intramolecular exchange of the agostic H atom between the two inequivalent P positions and at room-temperature reach a proton-catalyzed equilibrium with their hydride-bridged tautomers [ratio agostic/hydride = 10 (R = Cy), 30 (R = Et)]. The mixed-phosphide complex [Mo2Cp2(mu-PCy2)(mu-PPh2)(CO)2] behaves similarly, except that protonation now occurs specifically at the dicyclohexylphosphide ligand [ratio agostic/hydride = 0.5]. The reaction of the agostic complex [Mo2Cp2(mu-PCy2)(mu-kappa2-HPCy2)(CO)2]BF4 with CN(t)Bu gave mono- or disubstituted hydride derivatives [Mo2Cp2(mu-H)(mu-PCy2)2(CO)2-x(CNtBu)x]BF4 (Mo-Mo = 2.7901(7) A for x = 1). The photochemical removal of a CO ligand from the agostic complex also gives a hydride derivative, the triply bonded complex [Mo2Cp2(H)(mu-PCy2)2(CO)]BF4 (Mo-Mo = 2.537(2) A). Protonation of [Mo2Cp2(mu-PCy2)2(mu-CO)] gives the hydroxycarbyne derivative [Mo2Cp2(mu-COH)(mu-PCy2)2]BF4, which does not transform into its hydride isomer.

Synthesis, Characterization, and Interconversion of the Rhenium Polyhydrides [ReH3(η4-NP3)] and [ReH4(η4-NP3)]+ {NP3 = tris[2-(diphenylphosphanyl)ethyl]amine}

The rhenium(III) dichloride complex [ReCl2(η4-NP3)]Cl (1) was prepared from [ReCl3(CH3CN)(PPh3)2] by treatment with the tripodal tetradentate ligand N(CH2CH2PPh2)3 (NP3) in ethanol. The reaction of 1 with LiAlH4 in THF gave the rhenium(III) trihydride [ReH3(η4-NP3)] (2), which was converted into the rhenium(V) tetrahydride [ReH4(η4-NP3)]BPh4 (3) by protonation in CH2Cl2 with HBF4·OMe2, followed by a metathetical reaction with NaBPh4. The classical polyhydride nature of 2 and 3, as well as the overall molecular structures in solution, were determined by NMR spectroscopy, 1H NMR relaxation, and IR spectroscopy. The polyhydride complexes 2 and 3 are stereochemically nonrigid in solution, and the thermodynamic parameters associated with the fluxional processes were determined by variable-temperature NMR studies. A single-crystal X-ray analysis of 3 has shown the complex cation [ReH4(η4-NP3)]+ to be eight-coordinated by the four donor atoms of NP3 and by four terminal hydride ligands in a distorted dodecahedral geometry. An in situ IR study in CH2Cl2 has shown that the protonation of 3 occurs regioselectively at the metal center with no formation of a dihydrogen complex. Kinetic hydrogen bond products of the formula [(η4-NP3)H3Re···HOR] (ROH = C2H5OH, CFH2CH2OH, CF3CH2OH) were intercepted by IR spectroscopy at low temperature. The thermodynamic parameters associated with the formation of the hydrogen bond adducts were determined by either IR spectroscopy applying the Iogansen equation or van’t Hoff plots of the formation constant vs. temperature.

Synthesis, Characterization, and Interconversion of the Rhenium Polyhydrides [ReH3(η4-NP3)] and [ReH4(η4-NP3)]+ {NP3 = tris[2-(diphenylphosphanyl)ethyl]amine}

The rhenium(III) dichloride complex [ReCl2(η4-NP3)]Cl (1) was prepared from [ReCl3(CH3CN)(PPh3)2] by treatment with the tripodal tetradentate ligand N(CH2CH2PPh2)3 (NP3) in ethanol. The reaction of 1 with LiAIH4 in THF gave the rhenium(III) trihydride [ReH3(η4-NP3)] (2), which was converted into the rhenium(V) tetrahydride [ReH4(η4-NP3)]BPha4 (3) by protonation in CH2Cl2 with HBF4·OMe2, followed by a metathetical reaction with NaBPh4. The classical polyhydride nature of 2 and 3, as well as the overall molecular structures in solution, were determined by NMR spectroscopy, 1H NMR relaxation, and IR spectroscopy. The polyhydride complexes 2 and 3 are stereochemically nonrigid in solution, and the thermodynamic parameters associated with the fluxional processes were determined by variable-temperature NMR studies. A single-crystal X-ray analysis of 3 has shown the complex cation [ReH4 (qη4-NP3)]+ to be eight- coordinated by the four donor atoms of NP3 and by four terminal hydride ligands in a distorted dodecahedral geometry. An in situ IR study in CH2Cl2 has shown that the protonation of 3 occurs regioselectively at the metal center with no formation of a dihydrogen complex. Kinetic hydrogen bond products of the formula [(qη4NP3)H3Re··· HOR] (ROH = C2H5OH, CFH2CH2OH, CF3CH2OH) were intercepted by IR spectroscopy at low temperature. The thermodynamic parameters associated with the formation of the hydrogen bond adducts were determined by either IR spectroscopy applying the logansen equation or van't Hoff plots of the formation constant vs. temperature.