Synthesis and characterisation of homo- and hetero-trinuclear complexes containing the triply-bridging diphenylthiophosphinito [μ3-SPPh2]- ligand: Molecular structure of [Pd33-SPPh2)2(C 6F5)2(C6H4CH 2NMe2-2)...

Juan Forniés, Francisco Martinez, Rafael Navarro, Esteban P. Urriolabeitia, Alan J. Welch

Research output: Contribution to journalArticle

Abstract

Title full: Synthesis and characterisation of homo- and hetero-trinuclear complexes containing the triply-bridging diphenylthiophosphinito [µ3-SPPh2]- ligand: Molecular structure of [Pd33-SPPh2)2(C 6F5)2(C6H4CH 2NMe2-2)(PPh3)2]ClO 4·0.8CH2Cl2. The dinuclear complex [{Pd(µ-SPPh2)(C6F5)(PPh3)} 2] reacted with the cationic precursors [PdL(Me2CO)2]+[L = 2-(dimethylaminomethyl)phenyl-C1,N, quinolin-8-ylmethyl-C,N or phenylazophenyl-C1,N] and with the neutral precursors [M(C6F5)2(thf)2] (M = Pd or Pt, thf = tetrahydrofuran) to give the corresponding cationic homotrinuclear complexes [Pd33-SPPh2)2(C 6F5)2L-(PPh3)2]ClO 4 (L = C6H4CH2NMe2-2 1, NC9H6CH2-8 2 or PhN=NC6H4 3) and the neutral homo- and hetero-trinuclear complexes [Pd2M(µ3-SPPh2)2(C 6F5)4(PPh3)2] (M = Pd 4 or Pt 5) in which the [SPPh2]- group acts as a triply-bridging ligand. Complexes 1-5 have been characterized by spectroscopic methods (IR; 1H, 19F and 31P-{1H} NMR) and the molecular structure of [Pd33-SPPh2)2(C 6F5)2(C6H4CH 2NMe2-2)(PPh3)2]ClO4 1 has been determined crystallographically. Complex 1·0.8CH2Cl2 crystallizes in the monoclinic system, space group P21/c, a = 14.185(3), b = 21.589(4), c = 27.440(5) Å, ß = 104.95(3)° and Z = 4. The model refined to final values of R = 0.0702 and R' = 0.0849 for 5989 observed reflections [F > 4.0s(F)] and 860 parameters. The structure shows that the [Pd(µ-SPPh2)(C6F5)(PPh3)] 2 unit behaves as a cyclic bidentate sulfur ligand, co-ordinated to the [Pd(C6H4CH2NMe2-2)]+ group through the two S atoms. The central Pd3(SPPh2)2 cage contains two µ3-SPPh2 ligands linking the three palladium atoms.

Original languageEnglish
Pages (from-to)2805-2811
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number17
DOIs
Publication statusPublished - 1995

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