Reactions of monocyclopentadienyl pentafluorobenzenethiolato complexes of molybdenum and tungsten with group 11 metal derivatives: Crystal and molecular structures of [Au(PPh3)3][Mo(SC6F5) 45-C5H5)] and [Cu(PPh3)3][Mo(SC6F ...

Jack L. Davidson, W. Edward Lindsell, Kevin J. McCullough, Calum H. McIntosh

Research output: Contribution to journalArticle

Abstract

Full title: Reactions of monocyclopentadienyl pentafluorobenzenethiolato complexes of molybdenum and tungsten with group 11 metal derivatives: Crystal and molecular structures of [Au(PPh3)3][Mo(SC6F5) 4(?5-C5H5)] and [Cu(PPh3)3][Mo(SC6F5) 4(?5-C5H5)]. Displacement of coordinated Tl(I) as TlCl from [TlM(SC6F5)4Cp] (M = Mo, W; Cp = ?5-C5H5) by gold complexes [AuCl(PR3)] (R = Ph, Et) in dichloromethane or acetone solution affords ionic products [Au(PR3)3][M(SC6F5)4Cp], isolable in higher yields from reactions carried out in the presence of three molar equiv of free phosphine, PR3. Ligand exchange between [Au(PPh3)3][M(SC6F5)4Cp] and diphosphines produces derivatives [Au(Ph2P(CH2)n-PPh2) 2][M(SC6F5)4Cp] {n = 2 dppe (4); n = 3 dppp (5); M = Mo, W). A related reaction of [CuCl(PPh3)3] and [TlMo(SC6F5)4Cp] forms the copper derivative [Cu(PPh3)3][Mo(SC6F5) 4-Cp] as the major product. Attempts to isolate derivatives with group 11 metal cations coordinated by anions [M(SC6F5)4Cp]- have been unsuccessful. Molecular structures of crystalline bimetallic species [M'(PR3)3][Mo(SC6F5) 4Cp]·0.5CH2Cl2 {M' = Au (2a), Cu (6)} have been determined by X-ray diffraction and are essentially isomorphous. Both contain approximately trigonal-planar [M'(PPh3)3]+ cations with P-Au-P angles of 123.83(5)°, 122.28(5)°, and 113.62(5)° and an average Au-P distance 2.386(2) Å or P-Cu-P angles 121.24(7)°, 123.44(8)° and 115.11(7)° and an average Cu-P bond length 2.295(2) Å, respectively. The discrete anions [Mo(SC6F5)4Cp]- in 2a and 6 are similar, with "four-legged piano-stool" geometry and average Mo-S distances of 2.421(2) or 2.420(3) Å, respectively. Spectroscopic studies of complexes 4 and 5 support ionic constitutions with four-coordinated [Au((Ph2P(CH2)nPPh2) 2]+ cations. Variable temperature 19F NMR studies of anions [M(SC6F5)4Cp]- of gold derivatives give barriers to fluxional rotation/inversion of SC6F5 groups, ?G ca. 40-41 kJ mol-1 (208-228 K), M = Mo, or ?G ca. 43-44 kJ mol-1 (223-245 K), M = W, comparable with ?G values for salts [N(PPh3)2][M(SC6F5)4Cp], which are essentially independent of solvent (CD2Cl2, (CD3)2CO, or C6D5CD3), in contrast to barriers for coordinated species [TlM(SC6F5)4Cp]. © 1995 American Chemical Society.

Original languageEnglish
Pages (from-to)3497-3506
Number of pages10
JournalOrganometallics
Volume14
Issue number7
DOIs
Publication statusPublished - 1995

Fingerprint Dive into the research topics of 'Reactions of monocyclopentadienyl pentafluorobenzenethiolato complexes of molybdenum and tungsten with group 11 metal derivatives: Crystal and molecular structures of [Au(PPh<sub>3</sub>)<sub>3</sub>][Mo(SC<sub>6</sub>F<sub>5</sub>) <sub>4</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)] and [Cu(PPh<sub>3</sub>)<sub>3</sub>][Mo(SC<sub>6</sub>F ...'. Together they form a unique fingerprint.

  • Cite this