Transition metal–carbon bonds. Part XXXV. Internal metallation of t-butyldi-o-tolylarsine and di-t-butyl-o-tolylarsine by platinum

Abstract

t-Butyldi-o-tolylarsine (L′) and di-t-butyl-o-tolylarsine (L″) have been prepared. K₂PtCl₄ with L′(2 mol) gives trans-[PtCl₂L′₂] but when PtCl₂(PhCN)₂ was treated with L′(2 mol proportions) in boiling n-propanol the mono-metallated species [PtCl(As′–C)L′] was formed. With one mole proportion of L′PtCl₂(PhCN)₂ gives the chloro-bridged species [Pt₂Cl₂(As′–C)₂], [As′–Co(t-butyl-o-tolylarsino)benzyl]. The complexes [Pt₂(acetate)₂-(As′–C)₂], [Pt₂(benzoate)₂(As′–C)₂], [Pt(acac)(As′–C)], and [PtCl(As′–C)Q](Q = pyridine, PMe₂Ph, or AsMe₂Ph) and [Pt(As′–C)(PMe₂Ph)₂]Cl were prepared. On heating [PtCl₂(PhCN)₂] with L″[Pt₂Cl₂(As′–C)₂] forms {As″–CBu^t₂AsC₆H₃CH₂–}. Palladium complexes trans-[PdCl₂L′₂] and trans-[PdCl₂L″₂] were also prepared but could not be induced to internally metallate. ¹H n.m.r. and i.r. data are given.