Syntheses and characterisation of chloro(h3-allyl) dicarbonylmolybdenum(II) complexes of chiral and achiral ditertiaryphosphines

Joe G. Jesu Raj; Devendra D. Pathak; Pramesh N. Kapoor

doi:10.2478/s11532-011-0120-9

Syntheses and characterisation of chloro(h3-allyl) dicarbonylmolybdenum(II) complexes of chiral and achiral ditertiaryphosphines

Joe G. Jesu Raj, Devendra D. Pathak, Pramesh N. Kapoor

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

Abstract

A series of the complexes of the general formula [ClMo(CO) ₂(η ³-C₃H₅)(P-P)], [where (P-P) = (m-CH₃C₆H₄)₂P(CH₂) ₂PPh₂ (m-t-dppe); cis-Ph₂PCH=CHPPh₂ (cis-diphos); Ph₂PCH₂CH₂AsPh₂ (arsaphos); Ph₂P(CH₂)₄PPh₂ (dppb); (±)-1,2-C₆H₄(PMePh)₂ (rac-diphos); (2R,3R)Ph₂PC*H(Me)C*H(Me)PPh₂ (+)-chiraphos; (R,R)-Me₂C(O)₂{C*HCH₂PPh ₂}₂ (-)-diop] were synthesised by the reaction of the precursor complex [ClMo(CO)₂(η ³-C₃H ₅)(CH₃CN)₂] with the corresponding ditertiary phosphine in acetone. The complexes were isolated as yellow to orange air-stable solids and characterised by elemental analyses, FTIR and multinuclear NMR [¹H, ³¹P{¹H}] spectroscopic techniques. The carbonyl force constant values were calculated by Cotton and Kraihanzel approximate secular equations using ν _CΞO stretching frequencies observed in the FTIR and these were found to be 14.30-14.59 mdyne 0-A^-1 and 0.23-0.70 mdyne Å^-1 for K₁ and K_i respectively. Spectroscopic evidences have confirmed cis-octahedral structures for the synthesized complexes.

Original language	English
Pages (from-to)	165-171
Number of pages	7
Journal	Central European Journal of Chemistry
Volume	10
Issue number	1
DOIs	https://doi.org/10.2478/s11532-011-0120-9
State	Published - Feb 2012
Externally published	Yes

Keywords

Chelating ligands
Cotton and Kraihanzel approximations and allylic moiety
carbonyl force constants
phosphines

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10.2478/s11532-011-0120-9

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@article{eda6378bbf97473bb051518ae3561f47,

title = "Syntheses and characterisation of chloro(h3-allyl) dicarbonylmolybdenum(II) complexes of chiral and achiral ditertiaryphosphines",

abstract = "A series of the complexes of the general formula [ClMo(CO) 2(η 3-C3H5)(P-P)], [where (P-P) = (m-CH3C6H4)2P(CH2) 2PPh2 (m-t-dppe); cis-Ph2PCH=CHPPh2 (cis-diphos); Ph2PCH2CH2AsPh2 (arsaphos); Ph2P(CH2)4PPh2 (dppb); (±)-1,2-C6H4(PMePh)2 (rac-diphos); (2R,3R)Ph2PC*H(Me)C*H(Me)PPh2 (+)-chiraphos; (R,R)-Me2C(O)2{C*HCH2PPh 2}2 (-)-diop] were synthesised by the reaction of the precursor complex [ClMo(CO)2(η 3-C3H 5)(CH3CN)2] with the corresponding ditertiary phosphine in acetone. The complexes were isolated as yellow to orange air-stable solids and characterised by elemental analyses, FTIR and multinuclear NMR [1H, 31P{1H}] spectroscopic techniques. The carbonyl force constant values were calculated by Cotton and Kraihanzel approximate secular equations using ν CΞO stretching frequencies observed in the FTIR and these were found to be 14.30-14.59 mdyne 0-A-1 and 0.23-0.70 mdyne {\AA}-1 for K1 and Ki respectively. Spectroscopic evidences have confirmed cis-octahedral structures for the synthesized complexes.",

keywords = "Chelating ligands, Cotton and Kraihanzel approximations and allylic moiety, carbonyl force constants, phosphines",

author = "{Jesu Raj}, {Joe G.} and Pathak, {Devendra D.} and Kapoor, {Pramesh N.}",

note = "Funding Information: One of the authors, Joe Gerald Jesu Raj, is grateful to the Director, Indian School of Mines, Dhanbad for the award of research fellowship.",

year = "2012",

month = feb,

doi = "10.2478/s11532-011-0120-9",

language = "English",

volume = "10",

pages = "165--171",

journal = "Central European Journal of Chemistry",

issn = "1895-1066",

publisher = "Central European Science Journals",

number = "1",

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TY - JOUR

T1 - Syntheses and characterisation of chloro(h3-allyl) dicarbonylmolybdenum(II) complexes of chiral and achiral ditertiaryphosphines

AU - Jesu Raj, Joe G.

AU - Pathak, Devendra D.

AU - Kapoor, Pramesh N.

N1 - Funding Information: One of the authors, Joe Gerald Jesu Raj, is grateful to the Director, Indian School of Mines, Dhanbad for the award of research fellowship.

PY - 2012/2

Y1 - 2012/2

N2 - A series of the complexes of the general formula [ClMo(CO) 2(η 3-C3H5)(P-P)], [where (P-P) = (m-CH3C6H4)2P(CH2) 2PPh2 (m-t-dppe); cis-Ph2PCH=CHPPh2 (cis-diphos); Ph2PCH2CH2AsPh2 (arsaphos); Ph2P(CH2)4PPh2 (dppb); (±)-1,2-C6H4(PMePh)2 (rac-diphos); (2R,3R)Ph2PC*H(Me)C*H(Me)PPh2 (+)-chiraphos; (R,R)-Me2C(O)2{C*HCH2PPh 2}2 (-)-diop] were synthesised by the reaction of the precursor complex [ClMo(CO)2(η 3-C3H 5)(CH3CN)2] with the corresponding ditertiary phosphine in acetone. The complexes were isolated as yellow to orange air-stable solids and characterised by elemental analyses, FTIR and multinuclear NMR [1H, 31P{1H}] spectroscopic techniques. The carbonyl force constant values were calculated by Cotton and Kraihanzel approximate secular equations using ν CΞO stretching frequencies observed in the FTIR and these were found to be 14.30-14.59 mdyne 0-A-1 and 0.23-0.70 mdyne Å-1 for K1 and Ki respectively. Spectroscopic evidences have confirmed cis-octahedral structures for the synthesized complexes.

AB - A series of the complexes of the general formula [ClMo(CO) 2(η 3-C3H5)(P-P)], [where (P-P) = (m-CH3C6H4)2P(CH2) 2PPh2 (m-t-dppe); cis-Ph2PCH=CHPPh2 (cis-diphos); Ph2PCH2CH2AsPh2 (arsaphos); Ph2P(CH2)4PPh2 (dppb); (±)-1,2-C6H4(PMePh)2 (rac-diphos); (2R,3R)Ph2PC*H(Me)C*H(Me)PPh2 (+)-chiraphos; (R,R)-Me2C(O)2{C*HCH2PPh 2}2 (-)-diop] were synthesised by the reaction of the precursor complex [ClMo(CO)2(η 3-C3H 5)(CH3CN)2] with the corresponding ditertiary phosphine in acetone. The complexes were isolated as yellow to orange air-stable solids and characterised by elemental analyses, FTIR and multinuclear NMR [1H, 31P{1H}] spectroscopic techniques. The carbonyl force constant values were calculated by Cotton and Kraihanzel approximate secular equations using ν CΞO stretching frequencies observed in the FTIR and these were found to be 14.30-14.59 mdyne 0-A-1 and 0.23-0.70 mdyne Å-1 for K1 and Ki respectively. Spectroscopic evidences have confirmed cis-octahedral structures for the synthesized complexes.

KW - Chelating ligands

KW - Cotton and Kraihanzel approximations and allylic moiety

KW - carbonyl force constants

KW - phosphines

UR - http://www.scopus.com/inward/record.url?scp=83455169107&partnerID=8YFLogxK

U2 - 10.2478/s11532-011-0120-9

DO - 10.2478/s11532-011-0120-9

M3 - Article

AN - SCOPUS:83455169107

SN - 1895-1066

VL - 10

SP - 165

EP - 171

JO - Central European Journal of Chemistry

JF - Central European Journal of Chemistry

IS - 1

ER -

Syntheses and characterisation of chloro(h3-allyl) dicarbonylmolybdenum(II) complexes of chiral and achiral ditertiaryphosphines

Abstract

Keywords

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