Cp2Mo2 Research Articles

Cover Feature: Organometallic–Organic Hybrid Assemblies Featuring the Diantimony Complex [Cp2Mo2(CO)4(μ,η2‐Sb2)], AgI Ions and N‐Donor Molecules as Building Blocks (Chem. Eur. J. 35/2023)

The first supramolecular assemblies composed of the organometallic diantimony complex [(Cp)2Mo2(CO)4(μ,η2-Sb2)], AgI ions and various N-donor molecules are presented; the cover feature depicts the synthesis of these organometallic–organic aggregates as a fascinating, yet challenging, adventure. The crossroads in the middle reflects the dependency of the final product's structure and dimensionality (0D, 1D, or even 2D) on N-donor ligand choice and highlights the importance of fine tuning of the reaction conditions. More information can be found in the Research Article by M. Scheer and co-workers (DOI: 10.1002/chem.202300610).

Organometallic-Organic Hybrid Assemblies Featuring the Diantimony Complex [Cp2Mo2(CO)4(μ,η2-Sb2)], Ag(I) Ions and Ndonor Molecules as Building Blocks.

The reactions of the of the organometallic ligand complex [Cp2Mo2(CO)4(μ,η2-Sb2)] (C) with Ag[TEF] ([TEF]‾ = [Al{OC(CF3)3}4]‾) in the presence of a number of di- or polytopic N-donor molecules (1,6,7,12-tetraazaperylene (L1), 2,2'-bipyrimidine (L2), 4,4'-bipyridine (L3), trans-1,2-di(4-pyridyl)ethylene (L4)) and 1,3-di(4-pyridyl)propane (L5), were studied. These reactions lead, depending on the reaction stoichiometry and choice of linker, to the selective formation of dimeric or tetrameric supramolecular coordination complexes as well as 1D and 2D coordination polymers (CPs). The presented compounds are unique examples of supramolecular complexes incorporating both organometallic Sb-donor and organic N-donor molecules as ligands to stabilize metal ions. Moreover, one of the formed compounds, the CP [Ag4(η2:1-C)4(L4)4]n[TEF]4n, represents an exceptional 1D polymer incorporating both N- and Sb-donor ligands as connectors for metal ions.

Mixed Organometallic-Organic Hybrid Assemblies Based on the Diarsene Complex [Cp2 Mo2 (CO)4 (μ,η2 -As2 )], AgI Salts and N-Donor Organic Molecules.

The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(η2‐As2)] (1) with Ag[Al{OC(CF3)3}4] (Ag[TEF]) yielded the AgI monomer [Ag(η2‐1)3][TEF] (2). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic–organic hybrid assemblies upon its reaction with N‐donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2′‐bipyrimidine (L1) yielded the dicationic molecular compound [{(η2‐1)2Ag}2(μ‐L1)][TEF]2 (3) or the 1D polymer [{(η2‐1)Ag}(μ‐L1)]n[TEF]n (4) depending on the ratio of the reactants. However, its reactions with the pyridine‐based linkers 4,4′‐bipyridine (L2), 1,2‐bis(4‐pyridyl)ethylene (L3) and 1,2‐bis(4‐pyridyl)ethyne (L4) allowed the formation of the 2D polymers [{(η2‐1)Ag}2(μ‐Lx)3]n[TEF]2n [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step‐by‐step one‐pot reactions of 1, [Ag(CH3CN)3][Al{OC(CF3)2(CCl3)}4] ([Ag(CH3CN)3][TEFCl]) and linkers L2–L4 to produce the 2D polymers [{(η2‐1)Ag}2(μ,Lx)3]n[TEFCl]2n [Lx=L2 (8), L3 (9), L4 (10), respectively].

Discrete and polymeric organometallic-organic assemblies based on the diarsene complex [(Cp)2Mo2(CO)4(μ,η2-As2)], AgPF6and N-donor organic molecules

The first mixed-ligand self-assembly reactions of the diarsene complex [Cp2Mo2(CO)4(μ,η2-As2)] and N-donor organic molecules in the presence of AgPF6 allow for the synthesis of two discrete and four polymeric supramolecular aggregates.

Linking of CuI Units by Tetrahedral Mo2 E2 Complexes (E=P, As).

The reaction of [Cp2Mo2(CO)4(μ,η2:2‐E2)] (A: E=P, B: E=As, Cp=C5H5) with the WCA‐containing CuI salts ([Cu(CH3CN)4][Al{OC(CF3)3}4] (CuTEF, C), [Cu(CH3CN)4][BF4] (D) and [Cu(CH3CN)3.5][FAl{OC6F10(C6F5)}3] (CuFAl, E)) affords seven unprecedented coordination compounds. Depending on the E2 ligand complex, the counter anion of the copper salt and the stoichiometry, four dinuclear copper dimers and three trinuclear copper compounds are accessible. The latter complexes reveal first linear Cu3 arrays linked by E2 units (E=P, As) coordinated in an η2:1:1 coordination mode. All compounds were characterized by X‐ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. To define the nature of the Cu⋅⋅⋅Cu⋅⋅⋅Cu interactions, DFT calculations were performed.

The Potential of the Diarsene Complex [(C5 H5 )2 Mo2 (CO)4 (μ,η2 -As2 )] as a Connector Between Silver Ions.

The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(μ,η2‐As2)] (B) (Cp = C5H5) with Ag[FAl{OC6F10(C6F5)}3] (Ag[FAl]) and Ag[Al{OC(CF3)3}4] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η2‐B)4Ag2][FAl]2 (4), [(μ,η1:η2‐B)3(η2‐B)2Ag3][TEF]3 (5) and [(μ,η1:η2‐B)4Ag3][TEF]3 (6). These products are only composed of the complexes B and AgI. Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [AgI]3 units stabilized by organometallic bichelating ligands. According to DFT calculations, complex B coordinates to metal centers through both the As lone pair and the As−As σ‐bond thus showing this unique feature of this diarsene ligand.

The reaction behavior of [Cp2Mo2(CO)4(μ,η2:2-P2)] and [Cp''Ta(CO)2(η4-P4)] towards hydroxide and tert-butyl nucleophiles.

The reaction behavior of [Cp2Mo2(CO)4(μ,η2:2-P2)] (1) and [Cp''Ta(CO)2(η4-P4)] (2), respectively, towards the anions OH- and tBu- are reported. While the reaction of 1 with KOH gives the anionic complex [Cp2Mo2(CO)4(μ-PH2)]- (3) under a formal phosphorus atom abstraction, reaction with LitBu leads to the alkylation product [Cp2Mo2(CO)4(μ,η2:1-PPtBu)]- (4). The reactions of 2 with [IDipp-H][OH] ([IDipp-H]+ = 1,3-bis-(2,6-diisopropyl-phenyl)imidazolium) and LitBu yield [Cp''Ta(CO)2{η3-P4(O)H}]- (5) and [Cp''Ta(CO)2(η3-P4tBu)]- (6), respectively. Compounds 3, 4, 5 and 6 were comprehensively characterized by NMR spectroscopy and X-ray structure analysis.

The Potential of Molybdenum Complexes Bearing Unsubstituted Heterodiatomic Group 15 Elements as Linkers in Supramolecular Chemistry.

The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp2 Mo2 (CO)4 (μ,η2 :η2 -PE)] (Cp=C5 H5 ; E=As (1), Sb (2)), with CuI halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo2 PE units and the CuI halide, the oligomers [⟨{Cp2 Mo2 (CO)4 }{μ4 ,η2 :η2 :η2 :η1 -PE}⟩4 ⟨{CuX}{Cu(μ-X)}⟩2 ] (E=As (X=Cl (3), Br (4)); E=Sb (X=Cl (6), Br (7))) or the 1D coordination polymers [{Cp2 Mo2 (CO)4 }{μ4 ,η2 :η2 :η1 :η1 -PAs}{Cu(μ-I)}]n (5) and [{Cp2 Mo2 (CO)4 }{μ4 ,η2 :η2 :η2 :η1 -PSb}2 {Cu(μ-X)}3 ]n (X=I (8), Br (9)) are accessible. These solid-state aggregates are the first and only examples featuring the organometallic heterodiatomic Mo2 PE complexes 1 and 2 as linking moieties. DFT calculations demonstrate that complexes 1 and 2 present a unique class of mixed-donor ligands coordinating to CuI centers via the P lone pair and the P-E σ-bond, revealing an unprecedented coordination mode.

Use of Single-Metal Fragments for Cluster Building: Synthesis, Structure, and Bonding of Heterometallaboranes.

The synergic property of the CO ligand, in general, can stabilize metal complexes at lower oxidation states. Utilizing this feature of the CO ligand, we have recently isolated and structurally characterized a highly fluxional molybdenum complex [{Cp*Mo(CO)2}2{μ-η2:η2-B2H4}] (2; Cp* = η5-C5Me5) comprising the diborane(4) ligand. Compound 2 represents a rare class of bimetallic diborane(4) complex corresponding to a singly bridged C s structure. In an attempt to isolate the tungsten analogue of 2, [{Cp*W(CO)2}2{μ-η2:η2-B2H4}], we have isolated a rare vertex-fused cluster, [(Cp*W)3WB9H18] (5). Having a structural likeness with the dimolybdenum alkyne complex [{CpMo(CO)2}2C2H2], we have further explored the chemistry of 2 with CO gas that yielded a homoleptic trimolybdenum complex, [(Cp*Mo)3(μ-H)2(μ3-H)(μ-CO)2B4H4] (4). In an attempt to replace the 16-electron {Cp*MoH(CO)2} moiety in 4 with isolobal fragment {W(CO)5}, we treated the intermediate, obtained from the reaction of Cp*MoCl4 and LiBH4, with the monometal carbonyl fragment {W(CO)5·THF}. The reaction indeed yielded two bimetallic clusters, [(Cp*Mo)2B4H8W(CO)4] (7) and [(Cp*Mo)2B4H6W(CO)5] (8), that seem to have been generated by the replacement of one {BH} or {BH3} vertex from [(Cp*Mo)2B5H9], respectively. All of the compounds have been characterized by various spectroscopic analyses and single-crystal X-ray diffraction studies. Electron-counting rules and molecular orbital analyses provided further insight into the electronic structure of all of these molecules.

Crystal structure of the tetra-meth-yl(pheneth-yl)cyclo-penta-dienylmolybdenumtricarbonyl dimer.

The structure of the dimer bis-{tricarbon-yl[η5-tetra-meth-yl(pheneth-yl)cyclo-penta-dien-yl]molybdenum}(Mo-Mo), [Mo2(C17H21)2(CO)6], at 102 K has triclinic (P ) symmetry. The reaction between tetra-meth-yl(pheneth-yl)cyclo-penta-diene and molybdenum hexa-carbonyl in refluxing xylenes for 18 h led to a 56% yield of the dimer as a red solid. The asymmetric unit of the structure is the tetra-meth-yl(pheneth-yl)cyclo-penta-dienylmolybdenumtricarbonyl moiety and the entire dimeric mol-ecule is generated by inversion symmetry. The Mo-Mo bond length is 3.2773 (3) Å, a value slightly above the mean value for all [CpMo(CO)3]2 compounds listed in the CSD and slightly below the mean for [Cp*Mo(CO)3]2 complexes.

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W

The reaction of [(Cp*Mo)2 (μ-Cl)2 B2 H6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2 }2 {μ-η2 :η2 -B2 H4 }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO)2 }2 C2 H2 ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4 ] fragment, [{Cp*Mo(CO)2 }2 B2 H2 W(CO)4 ] (3) was isolated upon treatment with [W(CO)5 ⋅thf]. Compound 3 shows the intriguing presence of [B2 H2 ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO)2 }2 B2 H2 W(CO)4 ] (4) and [{Cp*W(CO)2 }2 B2 H2 Mo(CO)4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2.

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W

AbstractThe reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] (3) was isolated upon treatment with [W(CO)5⋅thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B−B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO)2}2B2H2W(CO)4] (4) and [{Cp*W(CO)2}2B2H2Mo(CO)4] (5), which provided direct proof of the existence of the tungsten analogue of 2.

Discrete and Polymeric Organometallic‐Organic Hybrid Materials Based on the Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)], CuI Salts, and 2,2′‐Bipyrimidine

The reaction of the diphosphorus complex [Cp2Mo2(CO)4(η2‐P2)] (1), with the CuI salts [Cu(CH3CN)4][BF4] or [Cu(CH3CN)4][PF6], and a mixture of [Cu(CH3CN)4][BF4] and CuCl in the presence of 2,2′‐bipyrimidine (2) is studied. Depending on the CuI salts used and the layering solvent involved in the crystallisation, a variety of novel coordination compounds are accessible in moderate to excellent yields (26–80 %): the novel dicationic molecular organometallic‐organic hybrid complexes [{Cp2Mo2(CO)4(µ3,η1:2:2‐P2)}4(µ2,η1:1:1:1‐C8H6N4)Cu2][BF4]2 (3) and [{Cp2Mo2(CO)4(µ3,η1:2:2‐P2)}2{Cp2Mo2(CO)4(µ3,η2:2:2‐P2)}2(µ2,η1:1:1:1‐C8H6N4)Cu2][PF6]2 (4), the unique neutral 1D organometallic‐organic hybrid polymer [{Cp2Mo2(CO)4(µ4,η1:1:2:2‐P2)}2(µ2,η1:1:1:1‐C8N6N4)(CuCl)2]n (5) and the unprecedented 2D organometallic‐organic hybrid polymer [{Cp2Mo2(CO)4(µ4,η1:1:2:2‐P2)}(µ2,η1:1:1:1‐C8H6N4){Cu2(µ‐Cl)}]2[BF4]2n (6).

Preorganized AgI Bimetallic Precursor with Labile Diphosphorus Ligands for a Programmed Synthesis of Organometallic-Organic Hybrid Polymers.

An AgI dimer capped with labile organometallic diphosphorus ligands [Cp2Mo2(CO)4(η2‐P2)] (Cp=C5H5) acts as a highly pre‐organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic–organic hybrid coordination polymers upon reaction with ditopic pyridine‐based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.

Strategies for the Construction of Supramolecular Dimers versus Homoleptic 1D Coordination Polymers Starting from the Diphosphorus [Cp2Mo2(CO)4(η2-P2)] Complex and Silver(I) Salts.

The reactions of the tetrahedral diphosphorus [Cp2Mo2(CO)4(η2‐P2)] (1; Cp = C5H5) complex with Ag[Al{OC(CF3)3}4] (AgTEF) (A) and Ag[FAl{OC(C6F5)(C6F10)}3] (AgFAl) (B) were studied. The first reaction led to the formation of the [Ag2(η2‐1)2(η1:η1‐1)2][TEF]2 (2) dimer and the [Ag2(η1:η1‐1)3]n[TEF]2n (3) coordination polymer, whereas the second reaction afforded the [Ag2(η1:η1‐1)2(η1‐CH2Cl2)2(η2‐C7H8)2][FAl]2 (4) or the [Ag2(η2‐1)2(η1:η1‐1)2][FAl]2 (5) dimer and the [Ag2(η1:η1‐1)4]n[FAl]2n (6) coordination polymer. In each case, the products obtained depended on the ratio of the reactants and/or the synthetic procedure.

Synthesis and structural characterization of trithiocarbonate complexes of molybdenum and ruthenium derived from CS2 ligand

In an effort to synthesize trithiocarbonate complexes of molybdenum and ruthenium, we carried out the reaction of CS2 with the intermediates, obtained from the reaction of [Cp#ML3X], (1: Cp# = C5Me5, M = Mo, L1 = L2 = L3 = CO, X = Me; 2: Cp# = C5H5, M = Ru, L1 = L2 = PPh3, X = Cl and 3: Cp# = C5H5, M = Fe, L1 = L2 = CO, X = I) and [LiBH4⋅thf]. The reactions led to formation of the trithiocarbonate complexes [Cp*Mo(CO)2(μ-ɳ2:ɳ1-CS3)(CO)3MoCp*] (4) [Cp*Mo(CO)2(ɳ2-S2CSMe)] (5) and [Cp*Mo(CO)2(ɳ2-S2CMe)] (6) in moderate yields. Treatment of [CpRu(PPh3)2Cl] (2) with [LiBH4⋅thf] followed by mild pyrolysis of CS2 yielded the trithiocarbonate ruthenium complex [CpRuPPh3(ɳ2-S2CSMe)] (7). All the new compounds have been characterized by various spectroscopic techniques and the structures of compounds 4, 5 and 7 were unequivocally established by crystallographic analysis.

The Diphosphorus Complex [Cp2Mo2(CO)4(η2-P2)] as a Building Block for the Synthesis of Mixed-Hybrid Coordination Polymers.

The three‐component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η2‐P2)] (1), with Ag[BF4] (2) in the presence of 2,2′‐bipyrimidine (3) leads to the formation of the two novel two‐dimensional networks 4 and 5. Compound 4 is a new two‐dimensional organometallic‐organic hybrid polymer, while derivative 5 represents a unique two‐dimensional organometallic‐inorganic‐organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two‐component reactions with organic molecules in addition of metal ions.

Heterometallic boride clusters of group 6 and 9 transition metals

Thermolysis of [Ru3(CO)12] with an in-situ generated intermediate, obtained from the reaction of [Cp*MoCl4] and [LiBH4.THF], led to the formation of [{Cp*Mo(CO)2}(μ4-B){Ru(CO)3}3(μ-H)2], 2 and [{Cp*Mo(CO)2}2(μ4-B){Ru(CO)3}2(μ-H)], 3 (Cp* = η5-C5Me5). In a similar fashion, when [Ru3(CO)12] was thermalized with [(Cp*Rh)2B2H6], obtained from a fast metathesis reaction of [Cp*RhCl2]2, 4 and [LiBH4.THF], yielded a novel heterometallic boride cluster [(Cp*Rh)(μ6-B){Ru(CO)3}4{RuH(CO)2}], 5. Both compounds 2 and 3 can be described as 50-cluster valence electron (cve) hetero-metallic boride clusters, in which the boron atom is in semi-interstitial position of a M4-butterfly geometry. Compound 5 contains 86 cluster valence-electrons, in which the boron atom is inside of an octahedral hole composed of one rhodium and five ruthenium atoms. Computational studies on the ground of density functional theory has been undertaken to analyze the bonding of 2, 3 and 5. The structural optimization yields geometries in agreement with the structure determinations and computed 11B chemical shifts accurately reflect the observed shifts. The molecular orbital analysis of them shows that all the valence orbitals of boron have been participated in bonding and therefore provides the “encapsulation” picture of the boron atom. All the compounds have been characterized by IR and 1H, 11B, and 13C NMR spectroscopy, and the geometries of the structures were unequivocally established by crystallographic analyses of compounds 2, 3 and 5.

Reactivity of [Cp*Mo(CO)3Me] with chalcogenated borohydrides Li[BH2E3] and Li[BH3EFc] (Cp*= (η 5-C5Me5); E = S, Se or Te; Fc = (C5H5-Fe-C5H4))

Reactivity of [Cp*Mo(CO) 3Me], 1 with various chalcogenide ligands such as Li[BH 2 E 3] and Li[BH 3EFc] (E = S, Se or Te; Fc = (C 5 H 5-Fe-C 5 H 4)) has been described. Room temperature reaction of 1 with Li[BH 2 E 3] (E = S and Se) yielded metal chalcogenide complexes [Cp*Mo(CO) 2(η 2-S 2 CCH 3)], 2 and [Cp*Mo(CO) 2(η 1-SeC 2 H 5)], 3. In compound 2, {Cp*Mo(CO) 2} fragment adopts a four-legged piano-stool geometry with a η 2-dithioacetate moiety. In contrast, treatment of 1 with Li[BH 3(EFc)] (E = S, Se or Te; Fc = C 5 H 5-Fe-C 5 H 4) yielded borate complexes [Cp*Mo(CO) 2(μ-H)(μ-EFc)BH 2], 4-6 in moderate yields. Compounds 4-6 are too unstable and gradual conversion to [{Cp*Mo(CO) 2} 2(μ-H)(μ-EFc] (7: E = S; 8: Se) and [{Cp*Mo(CO) 2} 2(μ-TeFc) 2], 9 happened by subsequent release of BH 3. All the compounds have been characterized by mass spectrometry, IR, multinuclear NMR spectroscopy and structures were unequivocally established by crystallographic analysis for compounds 2, 3 and 7. Reactivity of [Cp*Mo(CO)3Me] with various chalcogenide ligands such as, Li[BH2E3] and Li[BH3EFc] (E = S, Se or Te; Fc = (C5H5-Fe-C5H4)), generated novel molybdenum thiolate and agostic borate complexes respectively.

Coordination Complexes of Transition Metals (M = Mo, Fe, Rh, and Ru) with Tin(II) Phthalocyanine in Neutral, Monoanionic, and Dianionic States.

The ability of tin atoms to form stable Sn-M bonds with transition metals was used to prepare transition metal complexes with tin(II) phthalocyanine in neutral, monoanionic, and dianionic states. These complexes were obtained via the interactions of [Sn(IV)Cl2Pc(3-)](•-) or [Sn(II)Pc(3-)](•-) radical anions with {Cp*Mo(CO)2}2, {CpFe(CO)2}2, {CpMo(CO)3}2, Fe3(CO)12, {Cp*RhCl2}2, or Ph5CpRu(CO)2Cl. The neutral coordination complexes of Cp*MoBr(CO)2[Sn(II)Pc(2-)]·0.5C6H4Cl2 (1) and CpFe(CO)2[Sn(II)Pc(2-)]·2C6H4Cl2 (2) were obtained from [Sn(IV)Cl2Pc(3-)](•-). On the other hand, the coordination of transition metals to [Sn(II)Pc(3-)](•-) yielded anionic coordination complexes preserving the spin on [Sn(II)Pc(3-)](•-). However, in the case of {cryptand[2,2,2](Na(+))}{CpFe(II)(CO)2[Sn(II)Pc(4-)]}(-)·C6H4Cl2 (4), charge transfer from CpFe(I)(CO)2 to [Sn(II)Pc(3-)](•-) took place to form the diamagnetic [Sn(II)Pc(4-)](2-) dianion and {CpFe(II)(CO)2}(+). The complexes {cryptand[2,2,2](Na(+))}{Fe(CO)4[Sn(II)Pc(3-)](•-)} (5), {cryptand[2,2,2](Na(+))}{CpMo(CO)2[Sn(II)Pc(2-)Sn(II)Pc(3-)(•-)]} (6), and {cryptand[2,2,2](Na(+))}{Cp*RhCl2[Sn(II)Pc(3-)](•-)} (7) have magnetic moments of 1.75, 2.41, and 1.75 μ(B), respectively, owing to the presence of S = 1/2 spins on [Sn(II)Pc(3-)](•-) and CpMo(I)(CO)2 (for 6). In addition, the strong antiferromagnetic coupling of spins with Weiss temperatures of -35.5 -28.6 K was realized between the CpMo(I)(CO)2 and the [Sn(II)Pc(3-)](•-) units in 6 and the π-stacking {Fe(CO)4[Sn(II)Pc(3-)](•-)}2 dimers of 5, respectively. The [Sn(II)Pc(3-)](•-) radical anions substituted the chloride anions in Ph5CpRu(CO)2Cl to form the formally neutral compound {Ph5CpRu(II)(CO)2[Sn(II)Pc(3-)]} (8) in which the negative charge and spin are preserved on [Sn(II)Pc(3-)](•-). The strong antiferromagnetic coupling of spins with a magnetic exchange interaction J/k(B) = -183 K in 8 is explained by the close packing of [Sn(II)Pc(3-)](•-) in the π-stacked {Ph5CpRu(II)(CO)2[Sn(II)Pc(3-)](•-)}2 dimers.