Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane-Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds

The oxidative addition of (2,2‐dibromovinyl)ferrocene [Br2C=C(H)–Fc] (1) to [Pd(PPh3)4] yields the heterodinuclear σ‐alkenyl complex trans‐[{Pd(Br)(PPh3)2}–C(Br)=C(H)–Fc] (2). Nucleophilic attack of sodium thiolates on 1 unexpectedly affords the vinyl thioether derivatives (Z)‐[(RS)(H)C=C(H)–Fc] (4a: R = Ph; 4b: R = tBu; 4c: R = Et). Complexes 4a and 4c can also be prepared by addition of NaSR across the triple bond of Fc–C≡C–H (3). Addition of an excess of NaSR to 1 affords the dithioether derivatives (Z)‐[(RS)(H)C=C(SR)–Fc] (5a: R = Ph; 5b: R = p‐tolyl; 5c: R = Et). An addition/elimination sequence is suggested to account for this surprising result. The yield of 5c is very low due to a competing formation of ethynylferrocene (3). Reaction of 5b with [Re(thf)(CO)3(μ‐Br)]2 and [PtCl2(PhCN)2] leads to the heterodinuclear chelate complexes [Fc{C(S–p‐tolyl)=C(H)(S–p‐tolyl)}Re(Br)(CO)3] (6) and [Fc{C(S–p‐tolyl)=C(H)(S–p‐tolyl)}PtCl2] (7a), respectively. Metathesis of the fluxional compound 7a in the presence of NaI affords [Fc{C(S–p‐tolyl)=C(H)(S–p‐tolyl)}PtI2] (7b). The electrochemical properties of some of these complexes have been studied by means of cyclic voltammetry, and the molecular structures of 1, 2, 3, 4b, 4c and 6 have been determined by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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A‐Frame‐Containing Organometallic Oligomers Constructed From Homo‐ and Heterobimetallic M(μ‐dppm)₂M′ (M/M′ = Pd, Pt) Building Blocks

Clément

Aly

Husson

et al. 2009

Eur J Inorg Chem

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The homo-and heterodinuclear complexes XM(µ-dppm) 2 -MЈX (M = MЈ = Pd, X = Cl 1a; M = MЈ = Pd, X = I 1b; M = Pd, MЈ = Pt, X = Cl 2a; M = Pd, MЈ = Pt, X = I 2b; M = MЈ = Pt, X = Cl 3a; M = MЈ = Pt, X = I 3b) react with the diisocyanide ligand 1,2-bis(2-isocyanophenoxy)ethane (diNC) or the more soluble 1,2-bis(2-isocyano-4-tert-butylphenoxy)ethane (tBudiNC) in a 1:1 ratio to provide the thermally stable polymeric materials 4-9 {[XM(µ-dppm) 2 MЈ(µ-CN-C 6 H 3 R-2-OCH 2 -CH 2 O-2-C 6 H 3 R-NC)]X} n (M = MЈ = Pd, R = H, X = Cl 4a, I 4b; R = tBu, X = Cl 7; M = MЈ = Pt, R = H, X = Cl 5a, I 5b; R = tBu, X = Cl 8; M = Pd, MЈ = Pt, R = H, X = Cl 6a, I 6b; R = tBu, X = Cl 9).

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Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane-Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds

Cited by 17 publications

References 39 publications

Luminescent Organometallic Coordination Polymers Built on Isocyanide Bridging Ligands

Luminescent Organometallic Coordination Polymers Built on Isocyanide Bridging Ligands

(2,2‐Dibromovinyl)ferrocene as a Building Block for the Assembly of Heterodinuclear Complexes – Preparation of an σ‐Alkenylpalladium Complex and Dimetallic Dithioether Complexes

A‐Frame‐Containing Organometallic Oligomers Constructed From Homo‐ and Heterobimetallic M(μ‐dppm)₂M′ (M/M′ = Pd, Pt) Building Blocks

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Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane-Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds

Cited by 17 publications

References 39 publications

Luminescent Organometallic Coordination Polymers Built on Isocyanide Bridging Ligands

Luminescent Organometallic Coordination Polymers Built on Isocyanide Bridging Ligands

(2,2‐Dibromovinyl)ferrocene as a Building Block for the Assembly of Heterodinuclear Complexes – Preparation of an σ‐Alkenylpalladium Complex and Dimetallic Dithioether Complexes

A‐Frame‐Containing Organometallic Oligomers Constructed From Homo‐ and Heterobimetallic M(μ‐dppm)2M′ (M/M′ = Pd, Pt) Building Blocks

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A‐Frame‐Containing Organometallic Oligomers Constructed From Homo‐ and Heterobimetallic M(μ‐dppm)₂M′ (M/M′ = Pd, Pt) Building Blocks