Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF3COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)4(η5-C5H5)2]

Gillian A. Acum; Martin J. Mays; Paul R. Raithby; Gregory A. Solan

doi:10.1016/0022-328X(94)05268-G

Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF₃COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)₄(η⁵-C₅H₅)₂]

Gillian A. Acum, Martin J. Mays, Paul R. Raithby, Gregory A. Solan

University of Cambridge

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

Abstract

Some Group 6 transition metal complexes with bridging alkyne ligands [MM′(μ-HCCMe)(CO)₄(η⁵-C₅H₅)₂] [MM′ = W₂ 1; WMo 2; Mo₂ 3] and [WMo(μ-HCCPh)(CO)₄(η⁵-C₅H₅)₂] (5) were treated with hydrogen chloride to afford respectively [MM′Cl(μ-HCCHMe)(CO)₄(η⁵-C₅H₅)₂] [MM′=W₂ (6); WMo (7a); Mo₂ (8)] and [WMoCl(μ-HCCHPh)(CO)₄(η⁵-C₅H₅)₂] (9a). Similarly, the complexes [WMo(μ-HCCMe)(CO)₄(η⁵-C₅H₅)₂] (2) and [MM′(μ-HCCPh)(CO)₄(η⁵-C₅H₅)₂] [MM′=W₂ (4); WMo (5)] were treated with trifluoroacetic acid to give respectively [WMo(CF₃COO)(μ-HC=CHMe)(CO)₄(η⁵-C₅H₅)₂] (7b) and [MM′(CF₃COO)(μ-HC=CHPh)(CO)₄(η⁵-C₅H₅)₂] [MM′ = W₂ (10)]. All the products 6-10 result from anti Markovnikov addition of a proton to the bridging alkyne groups in 1-5, and contain (E)-alkenyl ligands, μ-HC=CHR, σ-bonded to one metal centre and π-bonded to the other. The metal centre to which the alkenyl ligand is σ-bonded in 6-10 is also coordinated by a conjugate base (Cl^- or CF₃COO^-). In the case of 9a a single-crystal X-ray diffraction study shows that the W centre has been formally oxidised from W(+1) to W(+3), with both the alkenyl and chloro groups σ-bonded to it, while the Mo centre is π-coordinated by the alkenyl group and remains in oxidation state (+1).

Original language	English
Pages (from-to)	65-72
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	492
Issue number	1
DOIs	https://doi.org/10.1016/0022-328X(94)05268-G
Publication status	Published - 19 Apr 1995

Bibliographical note

Funding Information:
We thank the EPSRC (G.A.A. and G.A.S.) for financial support.

Funding

We thank the EPSRC (G.A.A. and G.A.S.) for financial support.

Keywords

Alkenyl
Crystal structure
Molybdenum
Protonation
Tungsten

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/0022-328X(94)05268-G

Fingerprint

Dive into the research topics of 'Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF₃COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)₄(η⁵-C₅H₅)₂]'. Together they form a unique fingerprint.

Cite this

Acum, G. A., Mays, M. J., Raithby, P. R., & Solan, G. A. (1995). Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF₃COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)₄(η⁵-C₅H₅)₂]. Journal of Organometallic Chemistry, 492(1), 65-72. https://doi.org/10.1016/0022-328X(94)05268-G

Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF₃COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)₄(η⁵-C₅H₅)₂]. / Acum, Gillian A.; Mays, Martin J.; Raithby, Paul R. et al.
In: Journal of Organometallic Chemistry, Vol. 492, No. 1, 19.04.1995, p. 65-72.

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

Acum, GA, Mays, MJ, Raithby, PR & Solan, GA 1995, 'Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF₃COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)₄(η⁵-C₅H₅)₂]', Journal of Organometallic Chemistry, vol. 492, no. 1, pp. 65-72. https://doi.org/10.1016/0022-328X(94)05268-G

@article{c49c431d19a448979625e7cebc413d6d,

title = "Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF3COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)4(η5-C5H5)2]",

abstract = "Some Group 6 transition metal complexes with bridging alkyne ligands [MM′(μ-HCCMe)(CO)4(η5-C5H5)2] [MM′ = W2 1; WMo 2; Mo2 3] and [WMo(μ-HCCPh)(CO)4(η5-C5H5)2] (5) were treated with hydrogen chloride to afford respectively [MM′Cl(μ-HCCHMe)(CO)4(η5-C5H5)2] [MM′=W2 (6); WMo (7a); Mo2 (8)] and [WMoCl(μ-HCCHPh)(CO)4(η5-C5H5)2] (9a). Similarly, the complexes [WMo(μ-HCCMe)(CO)4(η5-C5H5)2] (2) and [MM′(μ-HCCPh)(CO)4(η5-C5H5)2] [MM′=W2 (4); WMo (5)] were treated with trifluoroacetic acid to give respectively [WMo(CF3COO)(μ-HC=CHMe)(CO)4(η5-C5H5)2] (7b) and [MM′(CF3COO)(μ-HC=CHPh)(CO)4(η5-C5H5)2] [MM′ = W2 (10)]. All the products 6-10 result from anti Markovnikov addition of a proton to the bridging alkyne groups in 1-5, and contain (E)-alkenyl ligands, μ-HC=CHR, σ-bonded to one metal centre and π-bonded to the other. The metal centre to which the alkenyl ligand is σ-bonded in 6-10 is also coordinated by a conjugate base (Cl- or CF3COO-). In the case of 9a a single-crystal X-ray diffraction study shows that the W centre has been formally oxidised from W(+1) to W(+3), with both the alkenyl and chloro groups σ-bonded to it, while the Mo centre is π-coordinated by the alkenyl group and remains in oxidation state (+1).",

keywords = "Alkenyl, Crystal structure, Molybdenum, Protonation, Tungsten",

author = "Acum, {Gillian A.} and Mays, {Martin J.} and Raithby, {Paul R.} and Solan, {Gregory A.}",

note = "Funding Information: We thank the EPSRC (G.A.A. and G.A.S.) for financial support.",

year = "1995",

month = apr,

day = "19",

doi = "10.1016/0022-328X(94)05268-G",

language = "English",

volume = "492",

pages = "65--72",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1",

}

TY - JOUR

T1 - Bridging alkenyl species from the protonation of ditungsten, tungsten-molybdenum and dimolybdenum transverse alkyne complexes with HCl and CF3COOH. Crystal structure of [WMoCl{μ-(E)-HCCHPh}(CO)4(η5-C5H5)2]

AU - Acum, Gillian A.

AU - Mays, Martin J.

AU - Raithby, Paul R.

AU - Solan, Gregory A.

N1 - Funding Information: We thank the EPSRC (G.A.A. and G.A.S.) for financial support.

PY - 1995/4/19

Y1 - 1995/4/19

N2 - Some Group 6 transition metal complexes with bridging alkyne ligands [MM′(μ-HCCMe)(CO)4(η5-C5H5)2] [MM′ = W2 1; WMo 2; Mo2 3] and [WMo(μ-HCCPh)(CO)4(η5-C5H5)2] (5) were treated with hydrogen chloride to afford respectively [MM′Cl(μ-HCCHMe)(CO)4(η5-C5H5)2] [MM′=W2 (6); WMo (7a); Mo2 (8)] and [WMoCl(μ-HCCHPh)(CO)4(η5-C5H5)2] (9a). Similarly, the complexes [WMo(μ-HCCMe)(CO)4(η5-C5H5)2] (2) and [MM′(μ-HCCPh)(CO)4(η5-C5H5)2] [MM′=W2 (4); WMo (5)] were treated with trifluoroacetic acid to give respectively [WMo(CF3COO)(μ-HC=CHMe)(CO)4(η5-C5H5)2] (7b) and [MM′(CF3COO)(μ-HC=CHPh)(CO)4(η5-C5H5)2] [MM′ = W2 (10)]. All the products 6-10 result from anti Markovnikov addition of a proton to the bridging alkyne groups in 1-5, and contain (E)-alkenyl ligands, μ-HC=CHR, σ-bonded to one metal centre and π-bonded to the other. The metal centre to which the alkenyl ligand is σ-bonded in 6-10 is also coordinated by a conjugate base (Cl- or CF3COO-). In the case of 9a a single-crystal X-ray diffraction study shows that the W centre has been formally oxidised from W(+1) to W(+3), with both the alkenyl and chloro groups σ-bonded to it, while the Mo centre is π-coordinated by the alkenyl group and remains in oxidation state (+1).

AB - Some Group 6 transition metal complexes with bridging alkyne ligands [MM′(μ-HCCMe)(CO)4(η5-C5H5)2] [MM′ = W2 1; WMo 2; Mo2 3] and [WMo(μ-HCCPh)(CO)4(η5-C5H5)2] (5) were treated with hydrogen chloride to afford respectively [MM′Cl(μ-HCCHMe)(CO)4(η5-C5H5)2] [MM′=W2 (6); WMo (7a); Mo2 (8)] and [WMoCl(μ-HCCHPh)(CO)4(η5-C5H5)2] (9a). Similarly, the complexes [WMo(μ-HCCMe)(CO)4(η5-C5H5)2] (2) and [MM′(μ-HCCPh)(CO)4(η5-C5H5)2] [MM′=W2 (4); WMo (5)] were treated with trifluoroacetic acid to give respectively [WMo(CF3COO)(μ-HC=CHMe)(CO)4(η5-C5H5)2] (7b) and [MM′(CF3COO)(μ-HC=CHPh)(CO)4(η5-C5H5)2] [MM′ = W2 (10)]. All the products 6-10 result from anti Markovnikov addition of a proton to the bridging alkyne groups in 1-5, and contain (E)-alkenyl ligands, μ-HC=CHR, σ-bonded to one metal centre and π-bonded to the other. The metal centre to which the alkenyl ligand is σ-bonded in 6-10 is also coordinated by a conjugate base (Cl- or CF3COO-). In the case of 9a a single-crystal X-ray diffraction study shows that the W centre has been formally oxidised from W(+1) to W(+3), with both the alkenyl and chloro groups σ-bonded to it, while the Mo centre is π-coordinated by the alkenyl group and remains in oxidation state (+1).

KW - Alkenyl

KW - Crystal structure

KW - Molybdenum

KW - Protonation

KW - Tungsten

UR - http://www.scopus.com/inward/record.url?scp=0037924193&partnerID=8YFLogxK

U2 - 10.1016/0022-328X(94)05268-G

DO - 10.1016/0022-328X(94)05268-G

M3 - Article

AN - SCOPUS:0037924193

SN - 0022-328X

VL - 492

SP - 65

EP - 72

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1

ER -