Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of...

Caroline M. Hay; Andrew D. Horton; Martin J. Mays; Paul R. Raithby

doi:10.1016/S0277-5387(00)86319-6

Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of...

Caroline M. Hay, Andrew D. Horton, Martin J. Mays, Paul R. Raithby

University of Cambridge

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

Abstract

Title full: Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of (η-C₅H₅)(CO)₂Mo(μ-PPh₂)Mn(η³-C₃H₅) (CO)₃ and (η-C₅H₅)(CO)Mo(μ-σ:η⁴- C₅H₉)(μ-PPh₂)Mn(CO)₃. The complex (η-C₅H₅)(CO)₂Mo(μ-H)(μ-PPh ₂)Mn(CO)₄ reacts under photolysis with the dienes allene, 1,1-dimethylallene, 1,3-butadiene and 2-methyl- 1,3-butadiene to give heterodimetallic allyl complexes in which the allyl ligand is bonded to either the Mn atom, the Mo atom or, alternatively, to both metal atoms. The crystal structure of two of these complexes, (η-C₅H₅)(CO)₂Mo(μ-PPh₂)Mn(η³-C₃H₅)(CO)₃ and (η-C₅H₅)(CO)Mo(μ-σ: η⁴-C₅H₉)(μ-PPh₂)Mn(CO )₃, have been determined by X-ray diffraction. In the former the allyl ligand is η³bonded to the manganese atom, which is also coordinated by three CO groups, the bridging PPh₂ group and the Mo atom [MoMn = 3.038(1) Å]. In the latter complex the syn-CH₃CHC(CH₃)CH₂ allyl ligand is η³bonded to the Mo atom and also via coordination of one CH bond of the CH₂ group to the Mn atom. The Mo atom is additionally coordinated by an η-C₅H₅ ligand, a CO group, the PPh₂ group and the Mn atom [MoMn = 2.800(1) Å]. In the presence of CO, the μ-allyl complexes are in equilibrium in solution with complexes of proposed formula (η-C₅H₅)(CO)(η³-allyl)Mo(μ-P Ph₂)Mn(CO)₄, containing the allyl ligand bonded exclusively to the Mo atom, but these latter complexes lose CO and revert to the μ-allyl complexes readily on attempted isolation. The μ-allyl complex (η-C₅H₅)(CO)Mo(μ-σ: η⁴-C₄H₇)Mn(CO)₃ gives a 1:1 adduct with P(OMe)₃ in which the coordination of the allyl CH bond to the Mn atom is replaced by bonding of the P(OMe)₃ group. The μ-allyl complexes can be deprotonated with LIBuⁿ giving anionic species which are postulated to contain μ-allylidene ligands. One such species, [(η-C₅H₅)(CO)Mo(μ-σ:η³ -CH₃CHCHCH)(η-PPh₂)Mn(CO)₃]^-, has been reacted with CD₃COOD to regenerate the corresponding allyl complex; the added deuterium atom is located exclusively at the site involved in the interaction with the Mn atom.

Original language	English
Pages (from-to)	987-999
Number of pages	13
Journal	Polyhedron
Volume	7
Issue number	10-11
DOIs	https://doi.org/10.1016/S0277-5387(00)86319-6
Publication status	Published - 31 Dec 1988

Funding

Acknowledgements-Wet hank Dr valuable discussion and the S.E.R.C. Limited for financial support.

Funders	Funder number
S.E.R.C. Limited

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0277-5387(00)86319-6

Cite this

@article{bf866584caa34ca19496b55f21b6b1ea,

title = "Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of...",

abstract = "Title full: Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of (η-C5H5)(CO)2Mo(μ-PPh2 )Mn(η3-C3H5) (CO)3 and (η-C5H5)(CO)Mo(μ-σ:η4- C5H9)(μ-PPh2)Mn(CO)3. The complex (η-C5H5)(CO)2Mo(μ-H)(μ-PPh 2)Mn(CO)4 reacts under photolysis with the dienes allene, 1,1-dimethylallene, 1,3-butadiene and 2-methyl- 1,3-butadiene to give heterodimetallic allyl complexes in which the allyl ligand is bonded to either the Mn atom, the Mo atom or, alternatively, to both metal atoms. The crystal structure of two of these complexes, (η-C5H5)(CO)2Mo(μ-PPh2 )Mn(η3-C3H5)(CO) 3 and (η-C5H5)(CO)Mo(μ-σ: η4-C5H9)(μ-PPh2)Mn(CO )3, have been determined by X-ray diffraction. In the former the allyl ligand is η3bonded to the manganese atom, which is also coordinated by three CO groups, the bridging PPh2 group and the Mo atom [MoMn = 3.038(1) {\AA}]. In the latter complex the syn-CH3CHC(CH3)CH2 allyl ligand is η3bonded to the Mo atom and also via coordination of one CH bond of the CH2 group to the Mn atom. The Mo atom is additionally coordinated by an η-C5H5 ligand, a CO group, the PPh2 group and the Mn atom [MoMn = 2.800(1) {\AA}]. In the presence of CO, the μ-allyl complexes are in equilibrium in solution with complexes of proposed formula (η-C5H5)(CO)(η3-allyl)Mo(μ-P Ph2)Mn(CO)4, containing the allyl ligand bonded exclusively to the Mo atom, but these latter complexes lose CO and revert to the μ-allyl complexes readily on attempted isolation. The μ-allyl complex (η-C5H5)(CO)Mo(μ-σ: η4-C4H7)Mn(CO)3 gives a 1:1 adduct with P(OMe)3 in which the coordination of the allyl CH bond to the Mn atom is replaced by bonding of the P(OMe)3 group. The μ-allyl complexes can be deprotonated with LIBun giving anionic species which are postulated to contain μ-allylidene ligands. One such species, [(η-C5H5)(CO)Mo(μ-σ:η3 -CH3CHCHCH)(η-PPh2)Mn(CO)3]- , has been reacted with CD3COOD to regenerate the corresponding allyl complex; the added deuterium atom is located exclusively at the site involved in the interaction with the Mn atom.",

author = "Hay, {Caroline M.} and Horton, {Andrew D.} and Mays, {Martin J.} and Raithby, {Paul R.}",

year = "1988",

month = dec,

day = "31",

doi = "10.1016/S0277-5387(00)86319-6",

language = "English",

volume = "7",

pages = "987--999",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier",

number = "10-11",

}

TY - JOUR

T1 - Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes

T2 - Crystal structures of...

AU - Hay, Caroline M.

AU - Horton, Andrew D.

AU - Mays, Martin J.

AU - Raithby, Paul R.

PY - 1988/12/31

Y1 - 1988/12/31

N2 - Title full: Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of (η-C5H5)(CO)2Mo(μ-PPh2 )Mn(η3-C3H5) (CO)3 and (η-C5H5)(CO)Mo(μ-σ:η4- C5H9)(μ-PPh2)Mn(CO)3. The complex (η-C5H5)(CO)2Mo(μ-H)(μ-PPh 2)Mn(CO)4 reacts under photolysis with the dienes allene, 1,1-dimethylallene, 1,3-butadiene and 2-methyl- 1,3-butadiene to give heterodimetallic allyl complexes in which the allyl ligand is bonded to either the Mn atom, the Mo atom or, alternatively, to both metal atoms. The crystal structure of two of these complexes, (η-C5H5)(CO)2Mo(μ-PPh2 )Mn(η3-C3H5)(CO) 3 and (η-C5H5)(CO)Mo(μ-σ: η4-C5H9)(μ-PPh2)Mn(CO )3, have been determined by X-ray diffraction. In the former the allyl ligand is η3bonded to the manganese atom, which is also coordinated by three CO groups, the bridging PPh2 group and the Mo atom [MoMn = 3.038(1) Å]. In the latter complex the syn-CH3CHC(CH3)CH2 allyl ligand is η3bonded to the Mo atom and also via coordination of one CH bond of the CH2 group to the Mn atom. The Mo atom is additionally coordinated by an η-C5H5 ligand, a CO group, the PPh2 group and the Mn atom [MoMn = 2.800(1) Å]. In the presence of CO, the μ-allyl complexes are in equilibrium in solution with complexes of proposed formula (η-C5H5)(CO)(η3-allyl)Mo(μ-P Ph2)Mn(CO)4, containing the allyl ligand bonded exclusively to the Mo atom, but these latter complexes lose CO and revert to the μ-allyl complexes readily on attempted isolation. The μ-allyl complex (η-C5H5)(CO)Mo(μ-σ: η4-C4H7)Mn(CO)3 gives a 1:1 adduct with P(OMe)3 in which the coordination of the allyl CH bond to the Mn atom is replaced by bonding of the P(OMe)3 group. The μ-allyl complexes can be deprotonated with LIBun giving anionic species which are postulated to contain μ-allylidene ligands. One such species, [(η-C5H5)(CO)Mo(μ-σ:η3 -CH3CHCHCH)(η-PPh2)Mn(CO)3]- , has been reacted with CD3COOD to regenerate the corresponding allyl complex; the added deuterium atom is located exclusively at the site involved in the interaction with the Mn atom.

AB - Title full: Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of (η-C5H5)(CO)2Mo(μ-PPh2 )Mn(η3-C3H5) (CO)3 and (η-C5H5)(CO)Mo(μ-σ:η4- C5H9)(μ-PPh2)Mn(CO)3. The complex (η-C5H5)(CO)2Mo(μ-H)(μ-PPh 2)Mn(CO)4 reacts under photolysis with the dienes allene, 1,1-dimethylallene, 1,3-butadiene and 2-methyl- 1,3-butadiene to give heterodimetallic allyl complexes in which the allyl ligand is bonded to either the Mn atom, the Mo atom or, alternatively, to both metal atoms. The crystal structure of two of these complexes, (η-C5H5)(CO)2Mo(μ-PPh2 )Mn(η3-C3H5)(CO) 3 and (η-C5H5)(CO)Mo(μ-σ: η4-C5H9)(μ-PPh2)Mn(CO )3, have been determined by X-ray diffraction. In the former the allyl ligand is η3bonded to the manganese atom, which is also coordinated by three CO groups, the bridging PPh2 group and the Mo atom [MoMn = 3.038(1) Å]. In the latter complex the syn-CH3CHC(CH3)CH2 allyl ligand is η3bonded to the Mo atom and also via coordination of one CH bond of the CH2 group to the Mn atom. The Mo atom is additionally coordinated by an η-C5H5 ligand, a CO group, the PPh2 group and the Mn atom [MoMn = 2.800(1) Å]. In the presence of CO, the μ-allyl complexes are in equilibrium in solution with complexes of proposed formula (η-C5H5)(CO)(η3-allyl)Mo(μ-P Ph2)Mn(CO)4, containing the allyl ligand bonded exclusively to the Mo atom, but these latter complexes lose CO and revert to the μ-allyl complexes readily on attempted isolation. The μ-allyl complex (η-C5H5)(CO)Mo(μ-σ: η4-C4H7)Mn(CO)3 gives a 1:1 adduct with P(OMe)3 in which the coordination of the allyl CH bond to the Mn atom is replaced by bonding of the P(OMe)3 group. The μ-allyl complexes can be deprotonated with LIBun giving anionic species which are postulated to contain μ-allylidene ligands. One such species, [(η-C5H5)(CO)Mo(μ-σ:η3 -CH3CHCHCH)(η-PPh2)Mn(CO)3]- , has been reacted with CD3COOD to regenerate the corresponding allyl complex; the added deuterium atom is located exclusively at the site involved in the interaction with the Mn atom.

UR - http://www.scopus.com/inward/record.url?scp=3843061912&partnerID=8YFLogxK

U2 - 10.1016/S0277-5387(00)86319-6

DO - 10.1016/S0277-5387(00)86319-6

M3 - Article

AN - SCOPUS:3843061912

SN - 0277-5387

VL - 7

SP - 987

EP - 999

JO - Polyhedron

JF - Polyhedron

IS - 10-11

ER -

Allyl and μ-allyl complexes from reactions of a hydrido-bridged molybdenum-manganese complex with dienes: Crystal structures of...

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this