Ma. Bennett et al., Complexes of platinum(II), platinum(IV), rhodium(III) and iridium(III) containing orthometallated triphenylphosphine, J CHEM S DA, (20), 2000, pp. 3537-3545
Citations number
57
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Treatment of [PtCl2(SEt2)(2)] or [RhCl3(SEt2)(3)] with 2-LiC6H4PPh2 gives f
our-membered ring chelate arylplatinum(II) or arylrhodium(III) complexes [P
t{C6H4(PPh2)-2}(2)] and [Rh{C6H4(PPh2)-2}(3)], respectively, whereas the co
rresponding reaction of [IrCl3(SEt2)(3)] gives IrCl{C6H4(PPh2)-2}(2)(PPh3)]
arising from cleavage of an Ir-C6H4(PPh2) bond. The chemistry of [Pt{C6H4(
PPh2)-2}(2)] is dominated by the lability of the Pt-P bonds, which are disp
laced sequentially by ligands at room temperature to give complexes contain
ing monodentate C6H4(PPh2), i.e. [Pt{C6H4(PPh2)-2}{eta(1)-C6H4(PPh2)-2}(L)]
[L = PPh3, P(OPh)(3), P(OMe)(3) or (BuNC)-N-t] and [Pt{eta(1)-C6H4(PPh2)-2
}(2)(R2PCH2CH2PR2)] (R = Ph, Me or Cy). In the cases of Me2PCH2CH2PMe2 and
Cy2PCH2CH2PCy2, binuclear intermediates can be detected in which these liga
nds bridge two platinum atoms. Oxidative addition of methyl iodide or iodin
e to [Pt{C6H4(PPh2)-2}(2)] gives initially platinum(IV) complexes [PtI(R){C
6H4(PPh2)-2}(2)] (R = Me or I) in which the added groups are mutually trans
; in the final, stable products the added groups and the phosphorus atoms a
re, separately, mutually cis. Oxidative addition of bromine to [Pt{C6H4(PPh
2)-2}(2)] gives initially trans-[PtBr2{C6H4(PPh2)-2}(2)] but subsequent oxi
dation and hydrolysis at the phosphorus atoms gives chelate tertiary phosph
ine oxide complexes of platinum(IV). The molecular structures of [Rh{C6H4(P
Ph2)-2}(3)] and cis-[PtI(Me){C6H4(PPh2)-2}(2)] have been determined by X-ra
y crystallography.