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Tris(2-methoxyphenyl) phosphite complexes of platinum(n): The cis preference of triaryl phosphite ligands and the effect of oxidation state on metal-phosphite bonding

DOI: 10.1039/DT9960001069

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1069 - 1076 (1996)

Update date:2022-07-31

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Authors:

Crispini, AlessandraCrispini, Alessandra

Harrison, Karl N.Harrison, Karl N.

Orpen, A. GuyOrpen, A. Guy

Pringle, Paul G.Pringle, Paul G.

Wheatcroft, James R.Wheatcroft, James R.

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Article abstract of DOI:10.1039/DT9960001069

The complexes cis-[PtX2{P(OC6H4OMe-2)3} 2] (X = Cl, Br or I) have been prepared by treatment of the corresponding [PtX2(cod)] (cod = cycloocta-1,5-diene) with P(OC6H4OMe-2)3. That with X = Cl reacted with 1 or 2 equivalents of SnCl2 to give cis-[PtCl(SnCl3){P(OC6H4OMe-2) 3}2] or trans-[Pt(SnCl3)2{P(OC6H4OMe-2) 3}2]. The unstable hydride trans-[PtH(Cl){P(OC6H4OMe-2)3}2] was detected when cis-[PtCl2{P(OC6H4OMe-2)3} 2] was treated with NaBH4 or [Pt{P(OC6H4OMe-2)3}3] with HCl. The organoplatinum complexes cis-[PtR2{P(OC6H4OMe-2)3} 2] and cis-[PtR(X){P(OC6H4OMe-2)3}2] (R = Me, X = Cl, I or CN; R = Et, X = Cl) were obtained from platinum-(II) and -(0) precursors. Addition of HBF4 to cis-[PtMe2{P(OC6H4OMe-2)3} 2], in the presence of H2O or MeCN, gave the cationic species cis-[PtMe(L){P(OC6H4OMe-2)3} 2][BF4] (L = H2O or MeCN). The significance of the observation that complexes of the type [PtMe(L){P(OC6H4OMe-2)3}2] are invariably cis is discussed. The crystal structures of cis-[PtCl2{P(OC6H4OMe-2)3} 2] and cis-[PtMe(OH2){P(OC6H4OMe-2)3} 2][BF4]·CH2Cl2 have been determined. These, together with those previously reported for P(OC6H4OMe-2)3 and [Pt(η-C2H4)-{P(OC6H4OMe-2) 3}2], show pronounced variation in P-O lengths and O-P-O bond angles consistent with the greater importance of Pt-P π bonding in the platinum(0) species. The phosphite P(OC6H4OMe-2)3 shows a range of conformations in the structures and that with anti, gauche, gauche (agg) conformation about the P-O bonds apparently favoured in general but ggg attainable in the absence of steric crowding. In cis-[PtMe(OH2){P(OC6H4OMe-2)3} 2][BF4]·CH2Cl2, intramolecular hydrogen bonding leads to an unusual aag conformation. Weak Pt ... O interactions involving the OMe groups of the phosphite ligand are observed in these structures. The correlation of P-O length and O-P-O angle variation is mirrored by similar behaviour for 133 Z-P(OPh)3 (Z = O, N or metal) structures. These observations are consistent with the now conventional view of M-P π bonding.

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Product name:Pt(CH3)(O(C2H5)2)(P(OC6H4OCH3)3)2(1+)*BF4(1-) = [Pt(CH3)(O(C2H5)2)(P(OC6H4OCH3)3)2]BF4

Cas No:176510-31-9

176510-31-9

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