Addition of some gold electrophiles to an octa-osmium carbonyl cluster: Thermodynamic vs. kinetic control

Zareen Akhter; Scott L. Ingham; Jack Lewis; Paul R. Raithby

doi:10.1016/0022-328X(94)84061-X

Addition of some gold electrophiles to an octa-osmium carbonyl cluster: Thermodynamic vs. kinetic control

Zareen Akhter, Scott L. Ingham, Jack Lewis, Paul R. Raithby

University of Cambridge

Research output: Contribution to journal › Article › peer-review

Abstract

The reaction of the dianionic cluster [PPN]₂[Os₈(CO)₂₂] {[PPN]⁺=[N(PPh₃)₂]⁺} with Au₂Cl₂L {L=chelating phosphines bis-(diphenylphosphino)methane (dppm), 1,2-bis-(diphenylphosphino)ethane (dppe) or 1,4-bis-(diphenylphosphino)butane (dppb)} in the presence of an excess of the halide acceptor TlPF₆, affords the neutral digold-substituted clusters [Os₈(CO)₂₂ (Au₂L)] {(1) L = dppm; (2) L = dppe; (3) L = dppb} in almost quantitative yield. The ³¹ P{1H} NMR spectra of these compounds indicate that the gold atoms are in non-equivalent environments and therefore cannot have a metal geometry similar to that previously reported for the related cluster [Os₈(CO)₂₂(AuPPh₃)₂]1 (4). A reinvestigation of the reaction between [PPN]₂ [Os₈(CO)₂₂] and monogold fragment 'AuPPh₃⁺' has shown that, in addition to (4), a second isomer of Os₈(CO)₂₂(AuPPh₃)₂] (5) is formed, which on the basis of the spectroscopic data is thought to have the same metal geometry as compounds (1-3). A single crystal X-ray diffraction study of the compound [Os₈(CO)₂₂(Au₂dppb)] (3) has shown that the metal core consists of a bicapped octahedron of osmium atoms, with one of the gold atoms capping the osmium octahedron, and the other gold atom bridging an edge of the osmium core.

Original language	English
Pages (from-to)	165-171
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	474
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(94)84061-X
Publication status	Published - 12 Jul 1994

Keywords

Carbonyl
Cluster
Crystal structure
Gold
Osmium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/0022-328X(94)84061-X

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@article{4bb41fcba47d4d33af7ee8da502cab4c,

title = "Addition of some gold electrophiles to an octa-osmium carbonyl cluster: Thermodynamic vs. kinetic control",

abstract = "The reaction of the dianionic cluster [PPN]2[Os8(CO)22] {[PPN]+=[N(PPh3)2]+} with Au2Cl2L {L=chelating phosphines bis-(diphenylphosphino)methane (dppm), 1,2-bis-(diphenylphosphino)ethane (dppe) or 1,4-bis-(diphenylphosphino)butane (dppb)} in the presence of an excess of the halide acceptor TlPF6, affords the neutral digold-substituted clusters [Os8(CO)22 (Au2L)] {(1) L = dppm; (2) L = dppe; (3) L = dppb} in almost quantitative yield. The 31 P{1H} NMR spectra of these compounds indicate that the gold atoms are in non-equivalent environments and therefore cannot have a metal geometry similar to that previously reported for the related cluster [Os8(CO)22(AuPPh3)2]1 (4). A reinvestigation of the reaction between [PPN]2 [Os8(CO)22] and monogold fragment 'AuPPh3+' has shown that, in addition to (4), a second isomer of Os8(CO)22(AuPPh3)2] (5) is formed, which on the basis of the spectroscopic data is thought to have the same metal geometry as compounds (1-3). A single crystal X-ray diffraction study of the compound [Os8(CO)22(Au2dppb)] (3) has shown that the metal core consists of a bicapped octahedron of osmium atoms, with one of the gold atoms capping the osmium octahedron, and the other gold atom bridging an edge of the osmium core.",

keywords = "Carbonyl, Cluster, Crystal structure, Gold, Osmium",

author = "Zareen Akhter and Ingham, {Scott L.} and Jack Lewis and Raithby, {Paul R.}",

year = "1994",

month = jul,

day = "12",

doi = "10.1016/0022-328X(94)84061-X",

language = "English",

volume = "474",

pages = "165--171",

journal = "Journal of Organometallic Chemistry",

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publisher = "Elsevier",

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TY - JOUR

T1 - Addition of some gold electrophiles to an octa-osmium carbonyl cluster

T2 - Thermodynamic vs. kinetic control

AU - Akhter, Zareen

AU - Ingham, Scott L.

AU - Lewis, Jack

AU - Raithby, Paul R.

PY - 1994/7/12

Y1 - 1994/7/12

N2 - The reaction of the dianionic cluster [PPN]2[Os8(CO)22] {[PPN]+=[N(PPh3)2]+} with Au2Cl2L {L=chelating phosphines bis-(diphenylphosphino)methane (dppm), 1,2-bis-(diphenylphosphino)ethane (dppe) or 1,4-bis-(diphenylphosphino)butane (dppb)} in the presence of an excess of the halide acceptor TlPF6, affords the neutral digold-substituted clusters [Os8(CO)22 (Au2L)] {(1) L = dppm; (2) L = dppe; (3) L = dppb} in almost quantitative yield. The 31 P{1H} NMR spectra of these compounds indicate that the gold atoms are in non-equivalent environments and therefore cannot have a metal geometry similar to that previously reported for the related cluster [Os8(CO)22(AuPPh3)2]1 (4). A reinvestigation of the reaction between [PPN]2 [Os8(CO)22] and monogold fragment 'AuPPh3+' has shown that, in addition to (4), a second isomer of Os8(CO)22(AuPPh3)2] (5) is formed, which on the basis of the spectroscopic data is thought to have the same metal geometry as compounds (1-3). A single crystal X-ray diffraction study of the compound [Os8(CO)22(Au2dppb)] (3) has shown that the metal core consists of a bicapped octahedron of osmium atoms, with one of the gold atoms capping the osmium octahedron, and the other gold atom bridging an edge of the osmium core.

AB - The reaction of the dianionic cluster [PPN]2[Os8(CO)22] {[PPN]+=[N(PPh3)2]+} with Au2Cl2L {L=chelating phosphines bis-(diphenylphosphino)methane (dppm), 1,2-bis-(diphenylphosphino)ethane (dppe) or 1,4-bis-(diphenylphosphino)butane (dppb)} in the presence of an excess of the halide acceptor TlPF6, affords the neutral digold-substituted clusters [Os8(CO)22 (Au2L)] {(1) L = dppm; (2) L = dppe; (3) L = dppb} in almost quantitative yield. The 31 P{1H} NMR spectra of these compounds indicate that the gold atoms are in non-equivalent environments and therefore cannot have a metal geometry similar to that previously reported for the related cluster [Os8(CO)22(AuPPh3)2]1 (4). A reinvestigation of the reaction between [PPN]2 [Os8(CO)22] and monogold fragment 'AuPPh3+' has shown that, in addition to (4), a second isomer of Os8(CO)22(AuPPh3)2] (5) is formed, which on the basis of the spectroscopic data is thought to have the same metal geometry as compounds (1-3). A single crystal X-ray diffraction study of the compound [Os8(CO)22(Au2dppb)] (3) has shown that the metal core consists of a bicapped octahedron of osmium atoms, with one of the gold atoms capping the osmium octahedron, and the other gold atom bridging an edge of the osmium core.

KW - Carbonyl

KW - Cluster

KW - Crystal structure

KW - Gold

KW - Osmium

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U2 - 10.1016/0022-328X(94)84061-X

DO - 10.1016/0022-328X(94)84061-X

M3 - Article

AN - SCOPUS:0011589534

SN - 0022-328X

VL - 474

SP - 165

EP - 171

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Addition of some gold electrophiles to an octa-osmium carbonyl cluster: Thermodynamic vs. kinetic control

Abstract

Keywords

ASJC Scopus subject areas

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