Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me)

Neil J. Browne; David Collison; Ruth Edge; Emma C. Fitzgerald; Madeleine Helliwell; Judith A K Howard; Hannah N. Lancashire; Paul J. Low; Joseph J W McDouall; James Raftery; Charlene A. Smith; Dmitry S. Yufit; Mark W. Whiteley

doi:10.1021/om901074b

Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me)

Neil J. Browne, David Collison, Ruth Edge, Emma C. Fitzgerald, Madeleine Helliwell, Judith A K Howard, Hannah N. Lancashire, Paul J. Low, Joseph J W McDouall, James Raftery, Charlene A. Smith, Dmitry S. Yufit, Mark W. Whiteley

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

Abstract

A series of molybdenum alkynyl complexes [Mo(C≡CR)(dppe)(η-C 7H7)] featuring a range of alkynyl substituents R with varying electron-donating and -withdrawing properties have been prepared. Oxidation of representative members of the series to the corresponding 17-electron radical cations has been achieved through both chemical oxidation and in situ spectroelectrochemical methods. The largely metal-centered character of the HOMO in this class of compounds has been established through a combination of experimental measurements (IR, UV-vis-NIR, EPR spectroscopies) and DFT-based calculations and rationalized in terms of the stabilization of the metal dxy, dyz, dxz, and dX2-y 2 through π- and δ-interactions with the C7H 7 ring and concomitant destablization of the d Z2 orbital. © 2010 American Chemical Society.

Original language	English
Pages (from-to)	1261-1276
Number of pages	15
Journal	Organometallics
Volume	29
Issue number	5
DOIs	https://doi.org/10.1021/om901074b
Publication status	Published - 8 Mar 2010

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CCDC 813159: Experimental Crystal Structure Determination
Brown, N. J. (Contributor), Collison, D. (Contributor), Edge, R. (Contributor), Fitzgerald, E. C. (Contributor), Helliwell, M. (Contributor), Howard, J. A. K. (Contributor), Lancashire, H. N. (Contributor), Low, P. J. (Contributor), Mcdouall, J. (Contributor), Raftery, J. (Contributor), Smith, C. A. (Contributor), Yufit, D. S. (Contributor) & Whiteley, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2011
DOI: 10.5517/ccw94y7, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccw94y7&sid=DataCite
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CCDC 813157: Experimental Crystal Structure Determination
Brown, N. J. (Contributor), Collison, D. (Contributor), Edge, R. (Contributor), Fitzgerald, E. C. (Contributor), Helliwell, M. (Contributor), Howard, J. A. K. (Contributor), Lancashire, H. N. (Contributor), Low, P. J. (Contributor), Mcdouall, J. (Contributor), Raftery, J. (Contributor), Smith, C. A. (Contributor), Yufit, D. S. (Contributor) & Whiteley, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2011
DOI: 10.5517/ccw94w5, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccw94w5&sid=DataCite
Dataset
CCDC 813160: Experimental Crystal Structure Determination
Brown, N. J. (Contributor), Collison, D. (Contributor), Edge, R. (Contributor), Fitzgerald, E. C. (Contributor), Helliwell, M. (Contributor), Howard, J. A. K. (Contributor), Lancashire, H. N. (Contributor), Low, P. J. (Contributor), Mcdouall, J. (Contributor), Raftery, J. (Contributor), Smith, C. A. (Contributor), Yufit, D. S. (Contributor) & Whiteley, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2011
DOI: 10.5517/ccw94z8, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccw94z8&sid=DataCite
Dataset

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Browne, N. J., Collison, D., Edge, R., Fitzgerald, E. C., Helliwell, M., Howard, J. A. K., Lancashire, H. N., Low, P. J., McDouall, J. J. W., Raftery, J., Smith, C. A., Yufit, D. S., & Whiteley, M. W. (2010). Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me). Organometallics, 29(5), 1261-1276. https://doi.org/10.1021/om901074b

@article{0df7906408974a3fb9c65f69b1258d16,

title = "Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me)",

abstract = "A series of molybdenum alkynyl complexes [Mo(C≡CR)(dppe)(η-C 7H7)] featuring a range of alkynyl substituents R with varying electron-donating and -withdrawing properties have been prepared. Oxidation of representative members of the series to the corresponding 17-electron radical cations has been achieved through both chemical oxidation and in situ spectroelectrochemical methods. The largely metal-centered character of the HOMO in this class of compounds has been established through a combination of experimental measurements (IR, UV-vis-NIR, EPR spectroscopies) and DFT-based calculations and rationalized in terms of the stabilization of the metal dxy, dyz, dxz, and dX2-y 2 through π- and δ-interactions with the C7H 7 ring and concomitant destablization of the d Z2 orbital. {\textcopyright} 2010 American Chemical Society.",

author = "Browne, {Neil J.} and David Collison and Ruth Edge and Fitzgerald, {Emma C.} and Madeleine Helliwell and Howard, {Judith A K} and Lancashire, {Hannah N.} and Low, {Paul J.} and McDouall, {Joseph J W} and James Raftery and Smith, {Charlene A.} and Yufit, {Dmitry S.} and Whiteley, {Mark W.}",

year = "2010",

month = mar,

day = "8",

doi = "10.1021/om901074b",

language = "English",

volume = "29",

pages = "1261--1276",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "5",

}

Browne, NJ, Collison, D, Edge, R, Fitzgerald, EC, Helliwell, M, Howard, JAK, Lancashire, HN, Low, PJ, McDouall, JJW, Raftery, J, Smith, CA, Yufit, DS & Whiteley, MW 2010, 'Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me)', Organometallics, vol. 29, no. 5, pp. 1261-1276. https://doi.org/10.1021/om901074b

Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me). / Browne, Neil J.; Collison, David; Edge, Ruth et al.
In: Organometallics, Vol. 29, No. 5, 08.03.2010, p. 1261-1276.

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

TY - JOUR

T1 - Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me)

AU - Browne, Neil J.

AU - Collison, David

AU - Edge, Ruth

AU - Fitzgerald, Emma C.

AU - Helliwell, Madeleine

AU - Howard, Judith A K

AU - Lancashire, Hannah N.

AU - Low, Paul J.

AU - McDouall, Joseph J W

AU - Raftery, James

AU - Smith, Charlene A.

AU - Yufit, Dmitry S.

AU - Whiteley, Mark W.

PY - 2010/3/8

Y1 - 2010/3/8

N2 - A series of molybdenum alkynyl complexes [Mo(C≡CR)(dppe)(η-C 7H7)] featuring a range of alkynyl substituents R with varying electron-donating and -withdrawing properties have been prepared. Oxidation of representative members of the series to the corresponding 17-electron radical cations has been achieved through both chemical oxidation and in situ spectroelectrochemical methods. The largely metal-centered character of the HOMO in this class of compounds has been established through a combination of experimental measurements (IR, UV-vis-NIR, EPR spectroscopies) and DFT-based calculations and rationalized in terms of the stabilization of the metal dxy, dyz, dxz, and dX2-y 2 through π- and δ-interactions with the C7H 7 ring and concomitant destablization of the d Z2 orbital. © 2010 American Chemical Society.

AB - A series of molybdenum alkynyl complexes [Mo(C≡CR)(dppe)(η-C 7H7)] featuring a range of alkynyl substituents R with varying electron-donating and -withdrawing properties have been prepared. Oxidation of representative members of the series to the corresponding 17-electron radical cations has been achieved through both chemical oxidation and in situ spectroelectrochemical methods. The largely metal-centered character of the HOMO in this class of compounds has been established through a combination of experimental measurements (IR, UV-vis-NIR, EPR spectroscopies) and DFT-based calculations and rationalized in terms of the stabilization of the metal dxy, dyz, dxz, and dX2-y 2 through π- and δ-interactions with the C7H 7 ring and concomitant destablization of the d Z2 orbital. © 2010 American Chemical Society.

U2 - 10.1021/om901074b

DO - 10.1021/om901074b

M3 - Article

SN - 0276-7333

VL - 29

SP - 1261

EP - 1276

JO - Organometallics

JF - Organometallics

IS - 5

ER -

Browne NJ, Collison D, Edge R, Fitzgerald EC, Helliwell M, Howard JAK et al. Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me). Organometallics. 2010 Mar 8;29(5):1261-1276. doi: 10.1021/om901074b

Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(C≡CR)(Ph2PCH 2CH2PPh2)(η-C7H 7)]n+ (n = O or 1; R = But, Fc, CO 2Me, or C6H4-4-X, X = NH2, OMe, Me, H, CHO, CO2Me)

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Datasets

CCDC 813159: Experimental Crystal Structure Determination

CCDC 813157: Experimental Crystal Structure Determination

CCDC 813160: Experimental Crystal Structure Determination

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