Three amide ligands of varying steric bulk and electronic properties were utilized to prepare a series of amido‐germanium(II)/tin(II) halide compounds, (LEX)n, (L= ‐N{B(DipNCH)2}(SiMe3), TBoL; ‐N{B(DipNCH)2}(SiPh3), PhBoL; ‐N(Dip)(tBu), DBuL; Dip=C6H3iPr2‐2,6; E=Ge or Sn; X=Cl or Br; n=1 or 2). Reductions of these with a magnesium(I) dimer, {(MesNacnac)Mg}2 (MesNacnac=[(MesNCMe)2CH]−, Mes=mesityl), afforded singly bonded amido‐digermynes (TBoLGe−GeTBoL and PhBoLGe−GePhBoL), and an amido‐distannyne (PhBoLSn−SnPhBoL), in addition to several low‐valent, amido stabilized tetrel–tetrel bonded cluster compounds, (DBuLGe)4, (DBuLSn)6 and Sn5(TBoL)4. The nature of the products resulting from these reactions was largely dependent on the steric bulk of the amide ligand employed. Cluster (DBuLGe)4 possessed an unusual folded butterfly structure, the bonding and electronic of which were examined using DFT calculations. Reactions of the amido‐germanium(I) compounds with H2 were explored, and gave rise to the amido‐digermene, TBoL(H)Ge=Ge(H)TBoL and the cyclotetragermane, {DBuL(H)Ge}4. Reactions of (DBuLGe)4 with a series of unsaturated small molecule substrates yielded DBuLGeOGeDBuL, DBuLGe(μ‐C2H4)2GeDBuL and DBuLGe(μ‐1,4‐C6H8)(μ‐1,2‐C6H8)GeDBuL. The latter results imply that (DBuLGe)4 can act as a masked source of the digermyne DBuLGeGeDBuL in these reactions. All further reactivity studies indicated that the germanium(I) compounds exhibit a “transition‐metal‐like” behavior, which is closely related to that previously described for bulky digermynes and related compounds.
Ion-pairing strongly influence the reactivity of low-oxidation state transition metalate anions, enabling the synthesis of novel phosphaorganometallic compounds.
Phosphorus analogues of the ubiquitous cyclopentadienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heavier group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopentadienyl anions SnP 4 2− and PbP 4 2− . The complexes [(η 4 -tBu 2 C 2 P 2 ) 2 Co 2 (μ,η 5 :η 5 − P 4 Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P 4 ) with cyclooctadiene cobalt complexes [Ar′TtCo(η 4 -P 2 C 2 tBu 2 )(η 4 −COD)] [Tt = Sn (2), Pb (3), Ar′ = C 6 H 3 -2,6{C 6 H 3 -2,6-iPr 2 } 2 , COD = cycloocta-1,5-diene] and Tt{Co(η 4 -P 2 C 2 tBu 2 )-(COD)} 2 [Tt = Sn (4), Pb (5)]. While the SnP 42− complex 6 was isolated as a pure and stable compound, compound 7 eliminated Pb(0) below room temperature to afford [(η 4 -tBu 2 C 2 P 2 ) 2 Co 2 (μ,η 4 :η 4 −P 4 ) (8), which is a rare example of a tripledecker complex with a P 4 2− middle deck. The electronic structures of 6−8 are analyzed using theoretical methods including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby, the aromatic nature of P 5 − and SnP 4 2− was confirmed, while for P 4 2− , a specific type of symmetry-induced weak paramagnetism was found that is distinct from conventional antiaromatic species.
This study details the isolation and characterisation of three novel silver(I) amides in solution and solidstate, [Ag(Cy 3 P)(HMDS)] 2,[ Ag(Cy 3 P){N(TMS)(Dipp)}] 3 and [Ag(Cy 3 P) 2 (NPh 2 )] 4.T heir catalytic abilities have proved successfuli nh ydroboration and hydrosilylation reactions with af ull investigation performed with complex 2.B oth protocols proceed under mild conditions, displaying exceptional functional-groupt olerance and chemoselectivity, in excellent conversions at competitive reactiont imes. This work reveals the first catalytic hydroboration of aldehydes and ketones performed by as ilver(I) catalyst.
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