The reactivity of a bis(μ-diphenylphosphido) dicyclopentadienyl dimolybdenum complex with an electron withdrawing ring substituent

Joanne C. Stichbury; Martin J. Mays; John E. Davies; Paul R. Raithby; Gregory P. Shields; Amanda G. Finch

doi:10.1016/S0020-1693(97)05490-X

The reactivity of a bis(μ-diphenylphosphido) dicyclopentadienyl dimolybdenum complex with an electron withdrawing ring substituent

Joanne C. Stichbury, Martin J. Mays, John E. Davies, Paul R. Raithby, Gregory P. Shields, Amanda G. Finch

University of Cambridge

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

8 Citations (SciVal)

Abstract

The synthesis of [(η⁵-C₅H₄CO₂Me) ₂Mo₂(CO)₆] (1), a bis(cyclopentadienyl) dimolybdenum complex with an electron withdrawing ring substituent, from the reaction of Mo(CO)₆ and [Na(C₅H₄CO₂Me)] is described. Complex 1 reacts thermally with P₂Ph₄ to form the bis(μ-diphenylphosphido) complex [(η⁵-C₅H₄CO₂Me) ₂Mo₂(μ-PPh₂)₂(CO)₂] (2). Air oxidation of 2 gives trans-[(η⁵-C₅H₄CO₂Me) ₂Mo₂(μ-PPh₂)₂(O)(CO)] (3a) and the corresponding cis-isomer 3b. The reactions of 3a and of the corresponding unsubstituted cyclopentadienyl complex [(η⁵-C₅H₅)₂Mo ₂(μ-PPh₂)₂(O)(CO)] (4) with [NO][BF₄], which yield respectively the nitrosyl substituted dimolybdenum complexes [(η⁵-C₅H₄CO₂Me) ₂Mo₂(μ-PPh₂)₂(O)(NO)][BF ₄] (5) and [(η⁵-C₅H₅)₂Mo ₂(μ-PPh₂)₂(O)(NO)][BF₄] (6), are described. Single crystal X-ray diffraction was used to determine the molecular structures of 1 (which crystallises in the monoclinic space group P2₁/c with a=9.811 (4), b=12.109 (2), c=9.919 (3) Å, β=110.00 (3)° and Z=2), 2 (which crystallises in the triclinic space group P1̄, a=13.364 (4), b=14.535 (4), c=10.576 (2) Å, α=91.33 (2), β=94.94 (2) γ=108.92 (2)° and Z=2) and 3a (which crystallises in the monoclinic space group P2₁/c with a=12.436 (2), b=15.300 (3), c=20.395 (4) Å, β=111.59 (3)° and Z=4).

Original language	English
Pages (from-to)	9-20
Number of pages	12
Journal	Inorganica Chimica Acta
Volume	262
Issue number	1
DOIs	https://doi.org/10.1016/S0020-1693(97)05490-X
Publication status	Published - 30 Sept 1997

Bibliographical note

Funding Information:
We wish to thank the EPSRC for financial support (J.E.D., G.P.S. and J.C.S.). We are grateful to the Cambridge Crystallographic Data Centre for a CASE award (G.P.S.).

Funding

We wish to thank the EPSRC for financial support (J.E.D., G.P.S. and J.C.S.). We are grateful to the Cambridge Crystallographic Data Centre for a CASE award (G.P.S.).

Keywords

Crystal structures
Dinuclear complexes
Molybdenum complexes
Nitrosyl complexes
Oxo complexes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0020-1693(97)05490-X

Cite this

@article{19e007c502fe465ba0878543be456681,

title = "The reactivity of a bis(μ-diphenylphosphido) dicyclopentadienyl dimolybdenum complex with an electron withdrawing ring substituent",

abstract = "The synthesis of [(η5-C5H4CO2Me) 2Mo2(CO)6] (1), a bis(cyclopentadienyl) dimolybdenum complex with an electron withdrawing ring substituent, from the reaction of Mo(CO)6 and [Na(C5H4CO2Me)] is described. Complex 1 reacts thermally with P2Ph4 to form the bis(μ-diphenylphosphido) complex [(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(CO)2] (2). Air oxidation of 2 gives trans-[(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(O)(CO)] (3a) and the corresponding cis-isomer 3b. The reactions of 3a and of the corresponding unsubstituted cyclopentadienyl complex [(η5-C5H5)2Mo 2(μ-PPh2)2(O)(CO)] (4) with [NO][BF4], which yield respectively the nitrosyl substituted dimolybdenum complexes [(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(O)(NO)][BF 4] (5) and [(η5-C5H5)2Mo 2(μ-PPh2)2(O)(NO)][BF4] (6), are described. Single crystal X-ray diffraction was used to determine the molecular structures of 1 (which crystallises in the monoclinic space group P21/c with a=9.811 (4), b=12.109 (2), c=9.919 (3) {\AA}, β=110.00 (3)° and Z=2), 2 (which crystallises in the triclinic space group P{\=1}, a=13.364 (4), b=14.535 (4), c=10.576 (2) {\AA}, α=91.33 (2), β=94.94 (2) γ=108.92 (2)° and Z=2) and 3a (which crystallises in the monoclinic space group P21/c with a=12.436 (2), b=15.300 (3), c=20.395 (4) {\AA}, β=111.59 (3)° and Z=4).",

keywords = "Crystal structures, Dinuclear complexes, Molybdenum complexes, Nitrosyl complexes, Oxo complexes",

author = "Stichbury, {Joanne C.} and Mays, {Martin J.} and {E. Davies}, John and Raithby, {Paul R.} and Shields, {Gregory P.} and Finch, {Amanda G.}",

note = "Funding Information: We wish to thank the EPSRC for financial support (J.E.D., G.P.S. and J.C.S.). We are grateful to the Cambridge Crystallographic Data Centre for a CASE award (G.P.S.).",

year = "1997",

month = sep,

day = "30",

doi = "10.1016/S0020-1693(97)05490-X",

language = "English",

volume = "262",

pages = "9--20",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier B.V.",

number = "1",

}

TY - JOUR

T1 - The reactivity of a bis(μ-diphenylphosphido) dicyclopentadienyl dimolybdenum complex with an electron withdrawing ring substituent

AU - Stichbury, Joanne C.

AU - Mays, Martin J.

AU - E. Davies, John

AU - Raithby, Paul R.

AU - Shields, Gregory P.

AU - Finch, Amanda G.

N1 - Funding Information: We wish to thank the EPSRC for financial support (J.E.D., G.P.S. and J.C.S.). We are grateful to the Cambridge Crystallographic Data Centre for a CASE award (G.P.S.).

PY - 1997/9/30

Y1 - 1997/9/30

N2 - The synthesis of [(η5-C5H4CO2Me) 2Mo2(CO)6] (1), a bis(cyclopentadienyl) dimolybdenum complex with an electron withdrawing ring substituent, from the reaction of Mo(CO)6 and [Na(C5H4CO2Me)] is described. Complex 1 reacts thermally with P2Ph4 to form the bis(μ-diphenylphosphido) complex [(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(CO)2] (2). Air oxidation of 2 gives trans-[(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(O)(CO)] (3a) and the corresponding cis-isomer 3b. The reactions of 3a and of the corresponding unsubstituted cyclopentadienyl complex [(η5-C5H5)2Mo 2(μ-PPh2)2(O)(CO)] (4) with [NO][BF4], which yield respectively the nitrosyl substituted dimolybdenum complexes [(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(O)(NO)][BF 4] (5) and [(η5-C5H5)2Mo 2(μ-PPh2)2(O)(NO)][BF4] (6), are described. Single crystal X-ray diffraction was used to determine the molecular structures of 1 (which crystallises in the monoclinic space group P21/c with a=9.811 (4), b=12.109 (2), c=9.919 (3) Å, β=110.00 (3)° and Z=2), 2 (which crystallises in the triclinic space group P1̄, a=13.364 (4), b=14.535 (4), c=10.576 (2) Å, α=91.33 (2), β=94.94 (2) γ=108.92 (2)° and Z=2) and 3a (which crystallises in the monoclinic space group P21/c with a=12.436 (2), b=15.300 (3), c=20.395 (4) Å, β=111.59 (3)° and Z=4).

AB - The synthesis of [(η5-C5H4CO2Me) 2Mo2(CO)6] (1), a bis(cyclopentadienyl) dimolybdenum complex with an electron withdrawing ring substituent, from the reaction of Mo(CO)6 and [Na(C5H4CO2Me)] is described. Complex 1 reacts thermally with P2Ph4 to form the bis(μ-diphenylphosphido) complex [(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(CO)2] (2). Air oxidation of 2 gives trans-[(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(O)(CO)] (3a) and the corresponding cis-isomer 3b. The reactions of 3a and of the corresponding unsubstituted cyclopentadienyl complex [(η5-C5H5)2Mo 2(μ-PPh2)2(O)(CO)] (4) with [NO][BF4], which yield respectively the nitrosyl substituted dimolybdenum complexes [(η5-C5H4CO2Me) 2Mo2(μ-PPh2)2(O)(NO)][BF 4] (5) and [(η5-C5H5)2Mo 2(μ-PPh2)2(O)(NO)][BF4] (6), are described. Single crystal X-ray diffraction was used to determine the molecular structures of 1 (which crystallises in the monoclinic space group P21/c with a=9.811 (4), b=12.109 (2), c=9.919 (3) Å, β=110.00 (3)° and Z=2), 2 (which crystallises in the triclinic space group P1̄, a=13.364 (4), b=14.535 (4), c=10.576 (2) Å, α=91.33 (2), β=94.94 (2) γ=108.92 (2)° and Z=2) and 3a (which crystallises in the monoclinic space group P21/c with a=12.436 (2), b=15.300 (3), c=20.395 (4) Å, β=111.59 (3)° and Z=4).

KW - Crystal structures

KW - Dinuclear complexes

KW - Molybdenum complexes

KW - Nitrosyl complexes

KW - Oxo complexes

UR - http://www.scopus.com/inward/record.url?scp=0001908981&partnerID=8YFLogxK

U2 - 10.1016/S0020-1693(97)05490-X

DO - 10.1016/S0020-1693(97)05490-X

M3 - Article

AN - SCOPUS:0001908981

SN - 0020-1693

VL - 262

SP - 9

EP - 20

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 1

ER -

The reactivity of a bis(μ-diphenylphosphido) dicyclopentadienyl dimolybdenum complex with an electron withdrawing ring substituent

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

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