Abstract
A series of neutral and anionic rhodium–germanium bonded compounds have been obtained by oxidative addition reactions, e.g. [(Ph3E)3RhCl + R3GeH →(Ph3E)2Rh(H)Cl(GeR3), E = P or As; R = Me, Et, or Cl]. Tributylstannane reacts similarly, but Me3SnH is decomposed to hydrogen and Me6Sn2. The RhIII products dissociate extensively in solution but are mostly air stable as solids. The complex (Ph3P)2Rh(H)Cl(GeEt3) loses Et3GeH on reaction with carbon monoxide or ethylene; with hydrogen chloride triethylchlorogermane is formed. Excess of HGeCl3 and (Ph3P)3RhCl give the phosphonium salt, [Ph3PH]3[Rh(GeCl3)6], and similar salts are formed by the reaction between HGeCl3 and RhCl3 in acid solution, e.g. [Me3NH]3[RhCl3(GeCl3)3]. Rhodium(I)–germanium complexes, (Ph3P)2(CO)Rh(GeCl3), (Ph3P)2(CO)2Rh(GeEt3), and [Rh(CO)Cl(GeCl3)2]2– have been isolated. Trichlorosilane and [(C8H12)RhCl]2 yield (C8H12)RhCl(SiCl3)2 whereas with (π-C5H5)Rh(C8H12) a cyclo-octene derivative, (π-C5H5)(C8H14) Rh(SiCl3)2 is formed.
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