The relationship between the molecular structure of [3,3-(PMe2Ph)2-closo-3,1,2-PtC2B9H11] and the mechanism of the fluxional behaviour of M(PR3)2-units in closo-twelve-atom metallaheteroboranes

Donnacha O'Connell; Trevor R. Spalding; George Ferguson; John F. Gallagher; John D. Kennedy

doi:10.1016/0022-328X(95)05718-5

The relationship between the molecular structure of [3,3-(PMe₂Ph)₂-closo-3,1,2-PtC₂B₉H₁₁] and the mechanism of the fluxional behaviour of M(PR₃)₂-units in closo-twelve-atom metallaheteroboranes

Donnacha O'Connell
, Trevor R. Spalding
, George Ferguson
, John F. Gallagher
, John D. Kennedy

School of Chemistry

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

Abstract

The upper limit of the free energy of the barrier to rotation of the platinum bis-phosphine unit in [3,3-(PMe₂Ph)₂-closo-3,1,2-PtC₂B₉H₁₁] 1 is 30< kJ mol^-1 in dichloromethane solution. This relatively low value is similar in magnitude to crystal-packing forces, and compound 1 crystallises from CH₂Cl₂-hexane solution as a 1 : 1 mixture of two different conformers with significantly different platinum-to-C₂B₃ bonding. These observations lead to the proposal of a general mechanism for the mutual rotation of {M(PR₃)₂} units above C₂B₉H₁₁.

Original language	English
Pages (from-to)	C12-C15
Journal	Journal of Organometallic Chemistry
Volume	503
Issue number	1
DOIs	https://doi.org/10.1016/0022-328X(95)05718-5
Publication status	Published - 1 Nov 1995

Keywords

Carborane
Crystal structure
Fluxionality
Mechanism
Metallacarborane
Platinum

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10.1016/0022-328X(95)05718-5

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O'Connell, D., Spalding, T. R., Ferguson, G., Gallagher, J. F., & Kennedy, J. D. (1995). The relationship between the molecular structure of [3,3-(PMe₂Ph)₂-closo-3,1,2-PtC₂B₉H₁₁] and the mechanism of the fluxional behaviour of M(PR₃)₂-units in closo-twelve-atom metallaheteroboranes. Journal of Organometallic Chemistry, 503(1), C12-C15. https://doi.org/10.1016/0022-328X(95)05718-5

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title = "The relationship between the molecular structure of [3,3-(PMe2Ph)2-closo-3,1,2-PtC2B9H11] and the mechanism of the fluxional behaviour of M(PR3)2-units in closo-twelve-atom metallaheteroboranes",

abstract = "The upper limit of the free energy of the barrier to rotation of the platinum bis-phosphine unit in [3,3-(PMe2Ph)2-closo-3,1,2-PtC2B9H11] 1 is 30< kJ mol-1 in dichloromethane solution. This relatively low value is similar in magnitude to crystal-packing forces, and compound 1 crystallises from CH2Cl2-hexane solution as a 1 : 1 mixture of two different conformers with significantly different platinum-to-C2B3 bonding. These observations lead to the proposal of a general mechanism for the mutual rotation of \{M(PR3)2\} units above C2B9H11.",

keywords = "Carborane, Crystal structure, Fluxionality, Mechanism, Metallacarborane, Platinum",

author = "Donnacha O'Connell and Spalding, \{Trevor R.\} and George Ferguson and Gallagher, \{John F.\} and Kennedy, \{John D.\}",

year = "1995",

month = nov,

day = "1",

doi = "10.1016/0022-328X(95)05718-5",

language = "English",

volume = "503",

pages = "C12--C15",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1",

}

O'Connell, D, Spalding, TR, Ferguson, G, Gallagher, JF & Kennedy, JD 1995, 'The relationship between the molecular structure of [3,3-(PMe₂Ph)₂-closo-3,1,2-PtC₂B₉H₁₁] and the mechanism of the fluxional behaviour of M(PR₃)₂-units in closo-twelve-atom metallaheteroboranes', Journal of Organometallic Chemistry, vol. 503, no. 1, pp. C12-C15. https://doi.org/10.1016/0022-328X(95)05718-5

The relationship between the molecular structure of [3,3-(PMe₂Ph)₂-closo-3,1,2-PtC₂B₉H₁₁] and the mechanism of the fluxional behaviour of M(PR₃)₂-units in closo-twelve-atom metallaheteroboranes. / O'Connell, Donnacha; Spalding, Trevor R.; Ferguson, George et al.
In: Journal of Organometallic Chemistry, Vol. 503, No. 1, 01.11.1995, p. C12-C15.

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

TY - JOUR

T1 - The relationship between the molecular structure of [3,3-(PMe2Ph)2-closo-3,1,2-PtC2B9H11] and the mechanism of the fluxional behaviour of M(PR3)2-units in closo-twelve-atom metallaheteroboranes

AU - O'Connell, Donnacha

AU - Spalding, Trevor R.

AU - Ferguson, George

AU - Gallagher, John F.

AU - Kennedy, John D.

PY - 1995/11/1

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N2 - The upper limit of the free energy of the barrier to rotation of the platinum bis-phosphine unit in [3,3-(PMe2Ph)2-closo-3,1,2-PtC2B9H11] 1 is 30< kJ mol-1 in dichloromethane solution. This relatively low value is similar in magnitude to crystal-packing forces, and compound 1 crystallises from CH2Cl2-hexane solution as a 1 : 1 mixture of two different conformers with significantly different platinum-to-C2B3 bonding. These observations lead to the proposal of a general mechanism for the mutual rotation of {M(PR3)2} units above C2B9H11.

AB - The upper limit of the free energy of the barrier to rotation of the platinum bis-phosphine unit in [3,3-(PMe2Ph)2-closo-3,1,2-PtC2B9H11] 1 is 30< kJ mol-1 in dichloromethane solution. This relatively low value is similar in magnitude to crystal-packing forces, and compound 1 crystallises from CH2Cl2-hexane solution as a 1 : 1 mixture of two different conformers with significantly different platinum-to-C2B3 bonding. These observations lead to the proposal of a general mechanism for the mutual rotation of {M(PR3)2} units above C2B9H11.

KW - Carborane

KW - Crystal structure

KW - Fluxionality

KW - Mechanism

KW - Metallacarborane

KW - Platinum

UR - https://www.scopus.com/pages/publications/4243626056

U2 - 10.1016/0022-328X(95)05718-5

DO - 10.1016/0022-328X(95)05718-5

M3 - Article

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SN - 0022-328X

VL - 503

SP - C12-C15

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1

ER -

The relationship between the molecular structure of [3,3-(PMe₂Ph)₂-closo-3,1,2-PtC₂B₉H₁₁] and the mechanism of the fluxional behaviour of M(PR₃)₂-units in closo-twelve-atom metallaheteroboranes

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Keywords

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