Coordination and organometallic chemistry of stibine ligands

Abstract

{CHio-C6H4CH2SbMe2)}z (VI), has been prepared indirectly by coupling of the di Grignard, o-C6H4(CH2MgCl)2 in concentrated thf solution followed by treatment with Me2SbCl, and directly by treatment of the {CH2(o-C6H4CH2MgCl)h with Me2SbCl. VI has been characterised by 1H and 13CeH} NMR spectroscopy and high resolution ElMS. Oxidation of VI with Br2 gives {CH2(o-C6H4CH2SbMe2Br2)}z. VI shows a strong tendency to function as a cis chelate in the complex [PtMe3I(VI)], forming an II-membered ring and providing a stable Pt(IV) stibine complex, to Pt(H) in the complex [PtCh(VI)] and to tungsten, in the complex [W(CO)4(VI)]. This is also confirmed by single crystal X-ray structure determinations of each of these complexes. The planar Pt(H) monomers [PtMe2(L-L)] and dimers [(PtMe2)z(L'-L')2] (L-L = R2Sb(CH2)3SbR2, o-C6H4(CH2SbMe2)2; L' -L' = R2SbCH2SbR2; R = Me or Ph) are obtained in good yield via reaction of [PtMe2(SMe2)2] with L-L or L'-L' in benzene. The Pt(IV) stibines, [PtMe3(L-L)I] (L-L = R2Sb(CH2)3SbR2, o-C6H4(CH2SbMe2)2 or 2 x SbPh3, SbMePh2 or SbMe2Ph) are obtained by treatment of [PtMe3I] with L-L in chloroform. The products have been characterised by 1H, 13CeH}, 195pt NMR spectroscopy, electrospray mass spectrometry and analysis. Crystal structure determinations on 5 representative Pt(IV) complexes confirm the distorted octahedral environment at Pt. The C1-distibines R2SbCH2SbR2 afford the dinuclear species, [(PtMe3)z().l-R2SbCH2SbR2)().l-I)2]. have [Rh( cod)(distibine)Cl], [Rh(cod)(distibine)]BF4' and [Rh(CO)(distibine)2][Rh(CO)2Ch] (distibine = R2Sb(CH2)3SbR2 , and o-C6H4(CH2SbMe2); R = Ph or Me) [Ir( cod)( distibine )]BF 4 and [Ir{Ph2Sb(CH2)3SbPh2}z]BF4 have also been prepared. The complexes have been characterised by 1H and 13C{lH} NMR and IR spectroscopy, electrospray mass spectrometry and microanalysis. The crystal structure of the anion exchanged [Rh(CO){Ph2Sb(CH2)3SbPh2}z]PFd/4CH2Ch is also described. [Rh{Ph2Sb(CH2)3SbPh2}z]BF4 synthesized. species been Ir(I) The [CoX2(o-C6H4(CH2PPh2)2)] (X = Cl, Br or I), [Rh(o-C6H4(CH2PPh2)2)2t, [M(cod)(o C6H4(CH2PPh2)2)t (M = Rh or Ir), [NiX2(o-C6H4(CH2PPh2)2)] (X = Cl or Br), [M'Ch(o C6H4(CH2PPh2)2)] (M' = Pd or Pt), [Pd2Ch(o-C6H4(CH2PPh2)2)2]2+, [Pd(o-C6H4(CH2PPh2)2)2]2+, [M"(o-C6H4(CH2PPh2)2)2t (M" = Cu, Ag or Au) and [(AuClMo-C6H4(CH2PPh2)2)] have been synthesised. Examples of Co(III), Ni(III) and Pt(IV) species are also repOlied. Where possible the products have been characterised by IR, UV-vis, NMR (H, 31p, 63CU and 195pt as appropriate) spectroscopies, mass spectrometry and microanalysis. Crystal structures of six representative examples are also described. The synthesis and characterisation of complexes of R2Sb(CH2)3SbR2 (R = Me or Ph) with a variety of metal carbonyls is described. These include cis-[M(CO)4 {R2Sb(CH2)3SbR2}] (M = Cr, Mo [{Ni(CO)3h{).l-R2Sb(CH2)3SbR2}], [C02(CO)dPh2Sb(CH2)3SbPh2}], and [Mn2(CO)8{Ph2Sb(CH2)3SbPh2}]. The complexes have been characterised by analysis, mass spectrometry, IR and multinuclear NMR spectroscopy as appropriate. [C02(CO)4 {Me2Sb(CH2)3SbMe2h] [Co(CO)4h [{Fe(CO)4h {).l-R2Sb(CH2)3SbR2}], or W), I1

More information

Identifiers

Catalogue record

Export record

ASCII CitationAtomBibTeXData Cite XMLDublin CoreDublin CoreEP3 XMLEndNoteHTML CitationHTML CitationHTML ListJSONMETSMODSMPEG-21 DIDLOpenURL ContextObjectOpenURL ContextObject in SpanRDF+N-TriplesRDF+N3RDF+XMLRIOXX2 XMLReferReference ManagerSimple Metadata