Metal Trimethylsilylthiolates for the Synthesis of Trinuclear MnPd₂ Complexes

Abstract

The manganese(II)‐palladium(II)‐sulfide complex [MnCl2(μ3‐S)2Pd2(dppp)2] (2) was prepared from the reaction of [PdCl2(dppp)] with [Li(N,N'‐tmeda)]2[Mn(SSiMe3)4] (2) in a 2:1 ratio under mild conditions. The new trimethylsilylthiolate complex [Pd(dppp)(SSiMe3)2] (3) was synthesized from the reaction of [Pd(dppp)(OAc)2] with two equivalents of Li[SSiMe3]; this was then used in a reaction with [Mn(CH3CN)2(OTf)2] to form the manganese(II)‐palladium(II)‐sulfide cluster [Mn(OTf)(thf)2(μ3‐S)2Pd2(dppp)2]OTf (4).

Chalcogenido‐Dimethylgallates and ‐Indates DMPyr2[Me2M(μ2−E)]2 (M=Ga, In; E=S, Se): Building Blocks for Higher and Lower Order Chalcogenidoindates

“…Complexes containing silylchalcogenido ligands [M−E−SiMe 3 ] are attractive synthons for condensation reactions e. g. with heterometal acetates M'OAc in order to selectively synthesize heteronuclear linkages M−E−M’ by elimination of Me 3 SiOAc [11,15,22–24] . For a long time, only two structural motives with heavy silylchalcogenido ligands were known: the spirocyclic compounds [(Me 2 M) 6 E(ESiMe 3 ) 4 ] (M=Ga, In; E=S, Se), [25] and [ i Pr 3 PCu( μ 3 2 −ESiMe 3 )(InMe 3 )] (E=S, Se): [26] The latter is the addition product of Me 3 In and i Pr 3 PCuESiMe 3 .…”

“…For a long time, only two structural motives with heavy silylchalcogenido ligands were known: the spirocyclic compounds [(Me 2 M) 6 E(ESiMe 3 ) 4 ] (M=Ga, In; E=S, Se), [25] and [ i Pr 3 PCu( μ 3 2 −ESiMe 3 )(InMe 3 )] (E=S, Se): [26] The latter is the addition product of Me 3 In and i Pr 3 PCuESiMe 3 . It unites all atoms necessary to act as single‐source precursor for CuIn(S x Se 1−x ) 2 materials [23,26] . Recently, we established a series of homoleptic trielates Cat[M(ESSiMe 3 ) 4 ] which can act as versatile precursors for binary (Cat + =organic cation) and ternary materials (Cat + =[Cu] + ) [7]…”

“…[21] Therefore, the charge of the chalcogen dianions is believed to be much better stabilized in gallium than in indium compounds. This prognosis is reflected in the observable higher reactivity of 5 and 6 towards amphoteric electrophiles such as Me 3 SiÀ E-SiMe [11,15,[22][23][24] For a long time, only two structural motives with heavy silylchalcogenido ligands were known: the spirocyclic compounds [(Me 2 M) 6 E(ESiMe 3 ) 4 ] (M=Ga, In; E=S, Se), [25] and [iPr 3 PCu(μ 32 À ESiMe 3 )(InMe 3 )] (E=S, Se): [26] The latter is the addition product of Me 3 In and iPr 3 PCuESiMe 3 . It unites all atoms necessary to act as single-source precursor for CuIn(S x Se 1À x ) 2 materials.…”

“…It unites all atoms necessary to act as single-source precursor for CuIn(S x Se 1À x ) 2 materials. [23,26] Recently, we established a series of homoleptic trielates Cat[M(ESSiMe 3 ) 4 ] which can act as versatile precursors for binary (Cat + = organic cation) and ternary materials (Cat + = [Cu] + ). [7] ure 11): This observation would be in accord with a fourmembered ring structure with either syn-or anti-[μ 2 À SÀ InMe 3 ] bridging groups.…”