Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph 2-7,8-nido-C2B9H8]2-

Susan Robertson; Rhona M. Garrioch; David Ellis; Thomas D. McGrath; Bruce E. Hodson; Georgina M. Rosair; Alan J. Welch

doi:10.1016/j.ica.2004.12.003

Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph ₂-7,8-nido-C₂B₉H₈]^2-

Susan Robertson, Rhona M. Garrioch, David Ellis, Thomas D. McGrath, Bruce E. Hodson, Georgina M. Rosair, Alan J. Welch

School of Engineering & Physical Sciences

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

22 Citations (Scopus)

Abstract

The reaction between [5-I-7,8-Ph₂-7,8-nido-C₂B ₉H₈]^2- and NiCl₂(dppe) affords 1,2-Ph₂-4,4-dppe-12-I-4,1,2-closo-NiC₂B₉H ₈ (1) and 1,8-Ph₂-2,2-dppe-10-I-2,1,8-closo-NiC ₂B₉H₈ (2). Reaction between the same carborane ligand and cis-PtCl₂(PMe₂Ph)₂ yields three species, 1,8-Ph₂-2,2-(PMe₂Ph)₂-10-I-2,1,8- closo-PtC₂B₉H₈ (3), 1,8-Ph₂-2,2- (PMe₂Ph)₂-12-I-2,1,8-closo-PtC₂B ₉H₈ (4), and 1,8-Ph₂-2,2-(PMe ₂Ph)₂-7-I-2,1,8-closo-PtC₂B₉H ₈ (5). Compounds 1-5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC₂B₉ architecture of 1 constitutes a "1,2 ? 1,2" cage C atom isomerisation, and the 2,1,8-MC₂B₉ architectures of 2-5 a 1,2 ? 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph₂-3,3-L₂-9-I-3,1,2-closo-MC₂B ₉H₈ [M = Ni, L₂ = dppe; M = Pt, L₂ = (PMe₂Ph)₂]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed. © 2004 Elsevier B.V. All rights reserved.

Original language	English
Pages (from-to)	1485-1493
Number of pages	9
Journal	Inorganica Chimica Acta
Volume	358
Issue number	5 SPEC. ISS.
DOIs	https://doi.org/10.1016/j.ica.2004.12.003
Publication status	Published - 15 Mar 2005

Keywords

Isomerisation mechanisms
Metallacarborane
NMR spectroscopy
Synthesis
Vertex labelling
X-ray crystallography

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Robertson, S., Garrioch, R. M., Ellis, D., McGrath, T. D., Hodson, B. E., Rosair, G. M., & Welch, A. J. (2005). Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph ₂-7,8-nido-C₂B₉H₈]^2-. Inorganica Chimica Acta, 358(5 SPEC. ISS.), 1485-1493. https://doi.org/10.1016/j.ica.2004.12.003

@article{8850d9832e30419f8745e0ef65f7b3fe,

title = "Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph 2-7,8-nido-C2B9H8]2-",

abstract = "The reaction between [5-I-7,8-Ph2-7,8-nido-C2B 9H8]2- and NiCl2(dppe) affords 1,2-Ph2-4,4-dppe-12-I-4,1,2-closo-NiC2B9H 8 (1) and 1,8-Ph2-2,2-dppe-10-I-2,1,8-closo-NiC 2B9H8 (2). Reaction between the same carborane ligand and cis-PtCl2(PMe2Ph)2 yields three species, 1,8-Ph2-2,2-(PMe2Ph)2-10-I-2,1,8- closo-PtC2B9H8 (3), 1,8-Ph2-2,2- (PMe2Ph)2-12-I-2,1,8-closo-PtC2B 9H8 (4), and 1,8-Ph2-2,2-(PMe 2Ph)2-7-I-2,1,8-closo-PtC2B9H 8 (5). Compounds 1-5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC2B9 architecture of 1 constitutes a {"}1,2 ? 1,2{"} cage C atom isomerisation, and the 2,1,8-MC2B9 architectures of 2-5 a 1,2 ? 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph2-3,3-L2-9-I-3,1,2-closo-MC2B 9H8 [M = Ni, L2 = dppe; M = Pt, L2 = (PMe2Ph)2]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed. {\textcopyright} 2004 Elsevier B.V. All rights reserved.",

keywords = "Isomerisation mechanisms, Metallacarborane, NMR spectroscopy, Synthesis, Vertex labelling, X-ray crystallography",

author = "Susan Robertson and Garrioch, {Rhona M.} and David Ellis and McGrath, {Thomas D.} and Hodson, {Bruce E.} and Rosair, {Georgina M.} and Welch, {Alan J.}",

year = "2005",

month = mar,

day = "15",

doi = "10.1016/j.ica.2004.12.003",

language = "English",

volume = "358",

pages = "1485--1493",

journal = "Inorganica Chimica Acta",

publisher = "Elsevier",

number = "5 SPEC. ISS.",

}

Robertson, S, Garrioch, RM, Ellis, D, McGrath, TD, Hodson, BE, Rosair, GM & Welch, AJ 2005, 'Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph ₂-7,8-nido-C₂B₉H₈]^2-', Inorganica Chimica Acta, vol. 358, no. 5 SPEC. ISS., pp. 1485-1493. https://doi.org/10.1016/j.ica.2004.12.003

Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph ₂-7,8-nido-C₂B₉H₈]^2-. / Robertson, Susan; Garrioch, Rhona M.; Ellis, David et al.
In: Inorganica Chimica Acta, Vol. 358, No. 5 SPEC. ISS., 15.03.2005, p. 1485-1493.

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

TY - JOUR

T1 - Towards the mechanism of heteroborane isomerisation

T2 - 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph 2-7,8-nido-C2B9H8]2-

AU - Robertson, Susan

AU - Garrioch, Rhona M.

AU - Ellis, David

AU - McGrath, Thomas D.

AU - Hodson, Bruce E.

AU - Rosair, Georgina M.

AU - Welch, Alan J.

PY - 2005/3/15

Y1 - 2005/3/15

N2 - The reaction between [5-I-7,8-Ph2-7,8-nido-C2B 9H8]2- and NiCl2(dppe) affords 1,2-Ph2-4,4-dppe-12-I-4,1,2-closo-NiC2B9H 8 (1) and 1,8-Ph2-2,2-dppe-10-I-2,1,8-closo-NiC 2B9H8 (2). Reaction between the same carborane ligand and cis-PtCl2(PMe2Ph)2 yields three species, 1,8-Ph2-2,2-(PMe2Ph)2-10-I-2,1,8- closo-PtC2B9H8 (3), 1,8-Ph2-2,2- (PMe2Ph)2-12-I-2,1,8-closo-PtC2B 9H8 (4), and 1,8-Ph2-2,2-(PMe 2Ph)2-7-I-2,1,8-closo-PtC2B9H 8 (5). Compounds 1-5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC2B9 architecture of 1 constitutes a "1,2 ? 1,2" cage C atom isomerisation, and the 2,1,8-MC2B9 architectures of 2-5 a 1,2 ? 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph2-3,3-L2-9-I-3,1,2-closo-MC2B 9H8 [M = Ni, L2 = dppe; M = Pt, L2 = (PMe2Ph)2]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed. © 2004 Elsevier B.V. All rights reserved.

AB - The reaction between [5-I-7,8-Ph2-7,8-nido-C2B 9H8]2- and NiCl2(dppe) affords 1,2-Ph2-4,4-dppe-12-I-4,1,2-closo-NiC2B9H 8 (1) and 1,8-Ph2-2,2-dppe-10-I-2,1,8-closo-NiC 2B9H8 (2). Reaction between the same carborane ligand and cis-PtCl2(PMe2Ph)2 yields three species, 1,8-Ph2-2,2-(PMe2Ph)2-10-I-2,1,8- closo-PtC2B9H8 (3), 1,8-Ph2-2,2- (PMe2Ph)2-12-I-2,1,8-closo-PtC2B 9H8 (4), and 1,8-Ph2-2,2-(PMe 2Ph)2-7-I-2,1,8-closo-PtC2B9H 8 (5). Compounds 1-5 have been characterised spectroscopically and crystallographically. The 4,1,2-MC2B9 architecture of 1 constitutes a "1,2 ? 1,2" cage C atom isomerisation, and the 2,1,8-MC2B9 architectures of 2-5 a 1,2 ? 1,7 cage C atom isomerisation, relative to the presumed first product of the metallations, 1,2-Ph2-3,3-L2-9-I-3,1,2-closo-MC2B 9H8 [M = Ni, L2 = dppe; M = Pt, L2 = (PMe2Ph)2]. The location of the (iodide) labelled boron vertex in the products allows speculation as to the mechanism of these isomerisations and the possible involvement of triangle face rotation is discussed. © 2004 Elsevier B.V. All rights reserved.

KW - Isomerisation mechanisms

KW - Metallacarborane

KW - NMR spectroscopy

KW - Synthesis

KW - Vertex labelling

KW - X-ray crystallography

UR - http://www.scopus.com/inward/record.url?scp=14644438555&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2004.12.003

DO - 10.1016/j.ica.2004.12.003

M3 - Article

VL - 358

SP - 1485

EP - 1493

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 5 SPEC. ISS.

ER -

Towards the mechanism of heteroborane isomerisation: 1,2 → 1,2 and 1,2 → 1,7 low-temperature isomerisations from metallations of [5-I-7,8-Ph ₂-7,8-nido-C₂B₉H₈]^2-

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