Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η4-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η4-C(CH2)3}(CO) 2(η-C5Me5)][BF4]

Stephen R. Allen; Stephen G. Barnes; Michael Green; Grainne Moran; Lynda Trollope; Nicholas W. Murrall; Alan J. Welch; Dima M. Sharaiha

doi:10.1039/DT9840001157

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅Me₅)][BF₄]

Stephen R. Allen^*
, Stephen G. Barnes
, Michael Green
, Grainne Moran
, Lynda Trollope
, Nicholas W. Murrall
, Alan J. Welch
, Dima M. Sharaiha

^*Corresponding author for this work

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

31 Citations (Scopus)

Abstract

Reaction of [Mo₂(CO)₆(η-C₅Me₅)₂] with methylenecyclopropane and AgBF₄ in CH₂Cl₂ affords the cationic trimethylenemethane complex [Mo{η⁴C(CH₂)₃}(CO)₂(η-C ₅Me₅)][BF₄]. Methylenecyclopropane and 2,2-dimethylmethylenecyclopropane react with Mo(NCMe)₂(CO)₂(η-C₅H₅)][BF ₄] to give [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅H₅)][BF₄] and [Mo{η⁴-C(CH₂)₂CMe₂}(CO) ₂(η-C₅H₅)][BF₄] respectively. A single-crystal X-ray diffraction study of [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅Me₅)][BF₄] confirmed that ring opening of methylenecyclopropane had occurred. The complex crystallises in the centrosymmetric orthorhombic space group Pbca with a = 12.822(2), b = 12.311 (3), c = 22.660(4) Å, and Z = 8 ion pairs. The structure has been solved by conventional methods and refined by full-matrix least squares to R = 0.0674 for 2 747 observed reflections at 268 ± 1 K. In the cation the trimethylenemethane ligand adopts an orientation that is syn with respect to the OC-Mo-CO angle. It is pyramidal with the CH₂ groups bent towards the molybdenum atom by an average of 12.4°. There is intramolecular congestion involving the C₅Me₅ and C(CH₂)₃ ligands that may contribute towards the observed asymmetric bonding of the former to the metal atom. Extended Hückel molecular-orbital calculations suggest, that the observed syn stereochemistry is electronically preferred, and that the barrier to rotation of the η⁴-C(CH₂)₃ ligand relative to a Mo(CO)₂(η-C₅H₅)⁺ fragment is high. The stereochemistry of the ring-opening reaction is disrotatory-out as exemplified by the conversion of cis-and trans-2,3-dimethylmethylenecyclopropane into syn,syn-dimethyl and syn,anti-dimethyl-trimethylene-methane complexes. The reaction of these cationic η⁴-trimethylenemethane complexes with the nucleophiles BH₄^-, OH^-, CuMe₂^-, and SPh^- affords η³-allylic complexes derived from attack on the peripheral carbons.

Original language	English
Pages (from-to)	1157-1169
Number of pages	13
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	6
DOIs	https://doi.org/10.1039/DT9840001157
Publication status	Published - 1984

ASJC Scopus subject areas

General Chemistry

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Allen, S. R., Barnes, S. G., Green, M., Moran, G., Trollope, L., Murrall, N. W., Welch, A. J., & Sharaiha, D. M. (1984). Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅Me₅)][BF₄]. Journal of the Chemical Society, Dalton Transactions, (6), 1157-1169. https://doi.org/10.1039/DT9840001157

Allen, Stephen R. ; Barnes, Stephen G. ; Green, Michael et al. / Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅Me₅)][BF₄]. In: Journal of the Chemical Society, Dalton Transactions. 1984 ; No. 6. pp. 1157-1169.

@article{0e0844543b114c4e854c787aada96634,

title = "Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η4-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo\{η4-C(CH2)3\}(CO) 2(η-C5Me5)][BF4]",

abstract = "Reaction of [Mo2(CO)6(η-C5Me5)2] with methylenecyclopropane and AgBF4 in CH2Cl2 affords the cationic trimethylenemethane complex [Mo\{η4C(CH2)3\}(CO)2(η-C 5Me5)][BF4]. Methylenecyclopropane and 2,2-dimethylmethylenecyclopropane react with Mo(NCMe)2(CO)2(η-C5H5)][BF 4] to give [Mo\{η4-C(CH2)3\}(CO) 2(η-C5H5)][BF4] and [Mo\{η4-C(CH2)2CMe2\}(CO) 2(η-C5H5)][BF4] respectively. A single-crystal X-ray diffraction study of [Mo\{η4-C(CH2)3\}(CO) 2(η-C5Me5)][BF4] confirmed that ring opening of methylenecyclopropane had occurred. The complex crystallises in the centrosymmetric orthorhombic space group Pbca with a = 12.822(2), b = 12.311 (3), c = 22.660(4) {\AA}, and Z = 8 ion pairs. The structure has been solved by conventional methods and refined by full-matrix least squares to R = 0.0674 for 2 747 observed reflections at 268 ± 1 K. In the cation the trimethylenemethane ligand adopts an orientation that is syn with respect to the OC-Mo-CO angle. It is pyramidal with the CH2 groups bent towards the molybdenum atom by an average of 12.4°. There is intramolecular congestion involving the C5Me5 and C(CH2)3 ligands that may contribute towards the observed asymmetric bonding of the former to the metal atom. Extended H{\"u}ckel molecular-orbital calculations suggest, that the observed syn stereochemistry is electronically preferred, and that the barrier to rotation of the η4-C(CH2)3 ligand relative to a Mo(CO)2(η-C5H5)+ fragment is high. The stereochemistry of the ring-opening reaction is disrotatory-out as exemplified by the conversion of cis-and trans-2,3-dimethylmethylenecyclopropane into syn,syn-dimethyl and syn,anti-dimethyl-trimethylene-methane complexes. The reaction of these cationic η4-trimethylenemethane complexes with the nucleophiles BH4-, OH-, CuMe2-, and SPh- affords η3-allylic complexes derived from attack on the peripheral carbons.",

author = "Allen, \{Stephen R.\} and Barnes, \{Stephen G.\} and Michael Green and Grainne Moran and Lynda Trollope and Murrall, \{Nicholas W.\} and Welch, \{Alan J.\} and Sharaiha, \{Dima M.\}",

year = "1984",

doi = "10.1039/DT9840001157",

language = "English",

pages = "1157--1169",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

number = "6",

}

Allen, SR, Barnes, SG, Green, M, Moran, G, Trollope, L, Murrall, NW, Welch, AJ & Sharaiha, DM 1984, 'Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅Me₅)][BF₄]', Journal of the Chemical Society, Dalton Transactions, no. 6, pp. 1157-1169. https://doi.org/10.1039/DT9840001157

Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅Me₅)][BF₄]. / Allen, Stephen R.; Barnes, Stephen G.; Green, Michael et al.
In: Journal of the Chemical Society, Dalton Transactions, No. 6, 1984, p. 1157-1169.

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

TY - JOUR

T1 - Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η4-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η4-C(CH2)3}(CO) 2(η-C5Me5)][BF4]

AU - Allen, Stephen R.

AU - Barnes, Stephen G.

AU - Green, Michael

AU - Moran, Grainne

AU - Trollope, Lynda

AU - Murrall, Nicholas W.

AU - Welch, Alan J.

AU - Sharaiha, Dima M.

PY - 1984

Y1 - 1984

N2 - Reaction of [Mo2(CO)6(η-C5Me5)2] with methylenecyclopropane and AgBF4 in CH2Cl2 affords the cationic trimethylenemethane complex [Mo{η4C(CH2)3}(CO)2(η-C 5Me5)][BF4]. Methylenecyclopropane and 2,2-dimethylmethylenecyclopropane react with Mo(NCMe)2(CO)2(η-C5H5)][BF 4] to give [Mo{η4-C(CH2)3}(CO) 2(η-C5H5)][BF4] and [Mo{η4-C(CH2)2CMe2}(CO) 2(η-C5H5)][BF4] respectively. A single-crystal X-ray diffraction study of [Mo{η4-C(CH2)3}(CO) 2(η-C5Me5)][BF4] confirmed that ring opening of methylenecyclopropane had occurred. The complex crystallises in the centrosymmetric orthorhombic space group Pbca with a = 12.822(2), b = 12.311 (3), c = 22.660(4) Å, and Z = 8 ion pairs. The structure has been solved by conventional methods and refined by full-matrix least squares to R = 0.0674 for 2 747 observed reflections at 268 ± 1 K. In the cation the trimethylenemethane ligand adopts an orientation that is syn with respect to the OC-Mo-CO angle. It is pyramidal with the CH2 groups bent towards the molybdenum atom by an average of 12.4°. There is intramolecular congestion involving the C5Me5 and C(CH2)3 ligands that may contribute towards the observed asymmetric bonding of the former to the metal atom. Extended Hückel molecular-orbital calculations suggest, that the observed syn stereochemistry is electronically preferred, and that the barrier to rotation of the η4-C(CH2)3 ligand relative to a Mo(CO)2(η-C5H5)+ fragment is high. The stereochemistry of the ring-opening reaction is disrotatory-out as exemplified by the conversion of cis-and trans-2,3-dimethylmethylenecyclopropane into syn,syn-dimethyl and syn,anti-dimethyl-trimethylene-methane complexes. The reaction of these cationic η4-trimethylenemethane complexes with the nucleophiles BH4-, OH-, CuMe2-, and SPh- affords η3-allylic complexes derived from attack on the peripheral carbons.

AB - Reaction of [Mo2(CO)6(η-C5Me5)2] with methylenecyclopropane and AgBF4 in CH2Cl2 affords the cationic trimethylenemethane complex [Mo{η4C(CH2)3}(CO)2(η-C 5Me5)][BF4]. Methylenecyclopropane and 2,2-dimethylmethylenecyclopropane react with Mo(NCMe)2(CO)2(η-C5H5)][BF 4] to give [Mo{η4-C(CH2)3}(CO) 2(η-C5H5)][BF4] and [Mo{η4-C(CH2)2CMe2}(CO) 2(η-C5H5)][BF4] respectively. A single-crystal X-ray diffraction study of [Mo{η4-C(CH2)3}(CO) 2(η-C5Me5)][BF4] confirmed that ring opening of methylenecyclopropane had occurred. The complex crystallises in the centrosymmetric orthorhombic space group Pbca with a = 12.822(2), b = 12.311 (3), c = 22.660(4) Å, and Z = 8 ion pairs. The structure has been solved by conventional methods and refined by full-matrix least squares to R = 0.0674 for 2 747 observed reflections at 268 ± 1 K. In the cation the trimethylenemethane ligand adopts an orientation that is syn with respect to the OC-Mo-CO angle. It is pyramidal with the CH2 groups bent towards the molybdenum atom by an average of 12.4°. There is intramolecular congestion involving the C5Me5 and C(CH2)3 ligands that may contribute towards the observed asymmetric bonding of the former to the metal atom. Extended Hückel molecular-orbital calculations suggest, that the observed syn stereochemistry is electronically preferred, and that the barrier to rotation of the η4-C(CH2)3 ligand relative to a Mo(CO)2(η-C5H5)+ fragment is high. The stereochemistry of the ring-opening reaction is disrotatory-out as exemplified by the conversion of cis-and trans-2,3-dimethylmethylenecyclopropane into syn,syn-dimethyl and syn,anti-dimethyl-trimethylene-methane complexes. The reaction of these cationic η4-trimethylenemethane complexes with the nucleophiles BH4-, OH-, CuMe2-, and SPh- affords η3-allylic complexes derived from attack on the peripheral carbons.

UR - https://www.scopus.com/pages/publications/37049109064

U2 - 10.1039/DT9840001157

DO - 10.1039/DT9840001157

M3 - Article

AN - SCOPUS:37049109064

SN - 1472-7773

SP - 1157

EP - 1169

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 6

ER -

Allen SR, Barnes SG, Green M, Moran G, Trollope L, Murrall NW et al. Reactions of co-ordinated ligands. Part 30. The transformation of methylenecyclopropanes into cationic η⁴-trimethylenemethanemolybdenum complexes, reactions with nucleophilic reagents, and the molecular structure of [Mo{η⁴-C(CH₂)₃}(CO) ₂(η-C₅Me₅)][BF₄]. Journal of the Chemical Society, Dalton Transactions. 1984;(6):1157-1169. doi: 10.1039/DT9840001157