Compounds of Germanium and Tin, 20. Stannylene Complexes of Iron and Nickel without Donor Stabilization

Abstract

Treatment of [Fe,(CO) Reports on unambiguously characterized transitionmetal stannylene complexes containing a tricoordinated tin atom are still scarce [2]. This is particularly apparent for complexes of the lighter transition metals with stannylenes that do not experience inter-or intramolecular stabilization from the free electron pairs of donor atoms"']. Thus, in the case of iron and nickel for example, the heterosubstituted iron-stannylene complex lr3] and the homoleptic, heterosubstituted nickel complex 2L41 were prepared and their structures elucidated.We recently prepared compound 3 as an example of a diarylstannylene lacking stabilization by donor atoms [5]. Although compound 3 is stable in the solid state, it undergoes irreversible rearrangement in solution to furnish the alkylarylstannylene 4, the formation of which was demonstrated indirectly by means of trapping reactions and preparation of the isotypic complexes [(OC)5M=SnRR'] where M = Cr, Mo, WL6,' 1. Large M-Sn bond lengths and small C -Sn--C bond angles are characteristic of these complexes and indicate that compound 4 behaves mainly as a o-donor in such compounds while its x-acceptor properties are only weakly effective. The different positions that a ligand can occupy in a trigonal bipyramid serve as a criterion for the evaluation of its donor or acceptor properties [s]. Hence, we attempted to prepare an iron complex of the type 1 and now report on the formation and structure of the stannylene complex 5 .

Transition Metal Complexes of (Schiff Base)Divalent Group 14 Element Species [(salen)M]n=M′(CO)6–n (n = 1, 2; M = Ge, Sn, Pb; M′ = Cr, W)

“…Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-136101 (5), 136102 (8), 136103 (11), and 136104 (14). Copies of the data can be obtained free of charge on application to the CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K. [Fax: (internat.)…”

Some Silicon, Germanium, Tin, and Lead Analogues of Carbenes, Alkenes, and Dienes

“…[56] sult arose from the reaction of the stannylene with [Fe 2 (CO) 9 ] or [Fe 3 (CO) 12 ]: In the resulting iron complex 68 the stannylene 67 occupies an axial site, indicative of a strong σ-donor but weak π-acceptor character. [64,65] A common feature of all distannenes 59, including the It is of interest to note that 66 represents the first strucrecently reported compound RRЈSnϭSnRRЈ [R ϭ Si(Si-turally characterized diarylstannylene that lacks donor sta-CH 3 ) 3 , RЈ ϭ 2,4,6-(CF 3 ) 3 C 6 H 2 ], [57] is their stability in the bilization. However, the stannylene [2,4,6-(CF 3 ) 3 C 6 H 2 ] 2 Sn:, crystalline state, even though they largely dissociate into stabilized by weak F···Sn contacts, was known previously stannylenes 60 in solution.…”

Nickel Coordination Compounds of Stanna‐closo‐dodecaborate

“…[3][4][5] Other systems, which feature nickel-tin bonds, are the recently described mixed-metal clusters [Sn 9 Ni 2 (CO)] 3-and [Ni 3 (µ-dppm) 3 (µ 3 -Cl)(µ 3 -SnCl 3 )]. [6,7] Furthermore, the homoleptic diaminostannylene compounds [M{Sn(NtBu) 2 SiMe 2 } 4 Cl 2 ] (M = Ni, Pd and Pt), which exhibit a square-planar coordination at the metal centers, were reported by Veith and co-workers. [8] The nickel complexes [Ni(SnPh 3 )(L)][BPh 4 ] [L = tris(2-diphenylphosphanylethyl)phosphane or tris(2-diphenylphosphanylethyl)amine] were found by the group of Sacconi, establishing the trigonal-bipyramidal coordination of nickel with polydentate phosphorus ligands and [SnPh 3 ] -.…”

“…[1,2] In general, nickel complexes with the metal atom in the formal oxidation states zero or two were treated with various tin ligands. Stannylenes for example react readily with the nickel(0) compounds [Ni(C 2 H 4 ) 3 ], [Ni(CO) 4 ] or bis-(toluene)nickel to give the respective (stannylene)nickel complexes. [3][4][5] Other systems, which feature nickel-tin bonds, are the recently described mixed-metal clusters [Sn 9 Ni 2 (CO)] 3-and [Ni 3 (µ-dppm) 3 (µ 3 -Cl)(µ 3 -SnCl 3 )].…”

“…Stannylenes for example react readily with the nickel(0) compounds [Ni(C 2 H 4 ) 3 ], [Ni(CO) 4 ] or bis-(toluene)nickel to give the respective (stannylene)nickel complexes. [3][4][5] Other systems, which feature nickel-tin bonds, are the recently described mixed-metal clusters [Sn 9 Ni 2 (CO)] 3-and [Ni 3 (µ-dppm) 3 (µ 3 -Cl)(µ 3 -SnCl 3 )]. [6,7] Furthermore, the homoleptic diaminostannylene compounds [M{Sn(NtBu) 2 SiMe 2 } 4 Cl 2 ] (M = Ni, Pd and Pt), which exhibit a square-planar coordination at the metal centers, were reported by Veith and co-workers.…”