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

Tungsten
Molybdenum
Molecular structure
Crystal structure
Metals
Derivatives
Anions
Cations
phosphine
Gold
Methylene Chloride
Bond length
Acetone
Copper
Salts
Nuclear magnetic resonance
Crystalline materials
Ligands
X ray diffraction
Geometry

Cite this

@article{5c5635ac048443ad9678a6b13175a5b0,
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(η5-C5H5)] and [Cu(PPh3)3][Mo(SC6F ...",
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) {\AA} 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) {\AA}, 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) {\AA}, 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]. {\circledC} 1995 American Chemical Society.",
author = "Davidson, {Jack L.} and Lindsell, {W. Edward} and McCullough, {Kevin J.} and McIntosh, {Calum H.}",
year = "1995",
doi = "10.1021/om00007a057",
language = "English",
volume = "14",
pages = "3497--3506",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "7",

}

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

In: Organometallics, Vol. 14, No. 7, 1995, p. 3497-3506.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reactions of monocyclopentadienyl pentafluorobenzenethiolato complexes of molybdenum and tungsten with group 11 metal derivatives

T2 - Crystal and molecular structures of [Au(PPh3)3][Mo(SC6F5) 4(η5-C5H5)] and [Cu(PPh3)3][Mo(SC6F ...

AU - Davidson, Jack L.

AU - Lindsell, W. Edward

AU - McCullough, Kevin J.

AU - McIntosh, Calum H.

PY - 1995

Y1 - 1995

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0012715567&partnerID=8YFLogxK

U2 - 10.1021/om00007a057

DO - 10.1021/om00007a057

M3 - Article

VL - 14

SP - 3497

EP - 3506

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 7

ER -