Synthesis, structure and substitution reactions of a heterodimetallic tungsten - manganese complex [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4]

Martin J. Mays; Steven M. Owen; Paul R. Raithby; Paul F. Reinisch; Gregory P. Shields; Gregory A. Solan

doi:10.1016/S0022-328X(96)06595-3

Synthesis, structure and substitution reactions of a heterodimetallic tungsten - manganese complex [(η⁵-C₅H₅)(OC)₂W( μ-H)( μ-PPh₂)Mn(CO)₄]

Martin J. Mays, Steven M. Owen, Paul R. Raithby, Paul F. Reinisch, Gregory P. Shields, Gregory A. Solan

University of Cambridge

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

5 Citations (SciVal)

Abstract

The room temperature reaction of [(η⁵-C₅H₅)W(CO)₃(PPh₂)] with [Mn(CO)₅] in tetrahydrofuran (THF) followed by protonation with H₃PO₄ gives [(η⁵-C₅H₅)(OC)₂W( μ-H)( μ-PPh₂)Mn(CO)₄] 1 as the major product. Among the identified minor products from this reaction are [Mn₂(CO)₉(PPh₂H)] 2a, [Mn₂(CO)₉(PPh₂PPh₂)] 2b, [Mn₂( μ-H)( μ-PPh₂)(CO)₈] 2c, and [Mn₂( μ-PPh₂)₂(CO)₈] 2d. ¹³CO reacts with complex 1 substituting both the manganese and tungsten carbonyl groups. In contrast, other two-electron donor ligands, L, only substitute the manganese carbonyl groups to give the substituted products [(η⁵-C₅H₅)(OC)₂W( μ-H)( μ-PPh₂)Mn(CO)₃L] (L = P(OMe)₃ 3a, PMe₂Ph 3b, PMePh₂ 3c, PPh₂H 3d), [(η⁵-C₅H₅)(OC)₂W( μ-H)( μ-PPh₂)Mn(CO)₂L₂] (L = P(OMe)₃ 4a or PMe₂Ph 4b). In the case of the photolytic reaction of 1 with the diphosphine, dppm (dppm = Ph₂PCH₂PPh₂), two products are obtained, one in which the ligand is chelated to the manganese centre, [(η⁵-C₅H₅)(OC)₂W( μ-H)( μ-PPh₂)Mn(CO)₂(dppm)] 5, and the other in which the ligand bridges the tungsten manganese centres, [(η⁵-C₅H₅)(OC)W( μ-H)( μ-PPh₂)( μ-dppm)Mn(CO)₃] 6. Conversion of complex 5 to 6 can be achieved by prolonged UV irradiation of 5. A single crystal X-ray diffraction study for [(η⁵-C₅H₅)(OC)₂W( μ-H)( μ-PPh₂)Mn(CO)₄] 1 is presented.

Original language	English
Pages (from-to)	123-134
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	528
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(96)06595-3
Publication status	Published - 1 Feb 1997

Bibliographical note

Funding Information:
We thank the EPSRC (S.M.O., P.F.R., G.P.S. and G.A.S.) for financial support.

Keywords

Crystal structure
Heterobimetallics
Hydrido
Manganese
Phosphido
Tungsten

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(96)06595-3

Cite this

@article{c146b8cbc80f45fab5dd5880fd53b3b2,

title = "Synthesis, structure and substitution reactions of a heterodimetallic tungsten - manganese complex [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4]",

abstract = "The room temperature reaction of [(η5-C5H5)W(CO)3(PPh2)] with [Mn(CO)5] in tetrahydrofuran (THF) followed by protonation with H3PO4 gives [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 as the major product. Among the identified minor products from this reaction are [Mn2(CO)9(PPh2H)] 2a, [Mn2(CO)9(PPh2PPh2)] 2b, [Mn2( μ-H)( μ-PPh2)(CO)8] 2c, and [Mn2( μ-PPh2)2(CO)8] 2d. 13CO reacts with complex 1 substituting both the manganese and tungsten carbonyl groups. In contrast, other two-electron donor ligands, L, only substitute the manganese carbonyl groups to give the substituted products [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)3L] (L = P(OMe)3 3a, PMe2Ph 3b, PMePh2 3c, PPh2H 3d), [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2L2] (L = P(OMe)3 4a or PMe2Ph 4b). In the case of the photolytic reaction of 1 with the diphosphine, dppm (dppm = Ph2PCH2PPh2), two products are obtained, one in which the ligand is chelated to the manganese centre, [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2(dppm)] 5, and the other in which the ligand bridges the tungsten manganese centres, [(η5-C5H5)(OC)W( μ-H)( μ-PPh2)( μ-dppm)Mn(CO)3] 6. Conversion of complex 5 to 6 can be achieved by prolonged UV irradiation of 5. A single crystal X-ray diffraction study for [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 is presented.",

keywords = "Crystal structure, Heterobimetallics, Hydrido, Manganese, Phosphido, Tungsten",

author = "Mays, {Martin J.} and Owen, {Steven M.} and Raithby, {Paul R.} and Reinisch, {Paul F.} and Shields, {Gregory P.} and Solan, {Gregory A.}",

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

year = "1997",

month = feb,

day = "1",

doi = "10.1016/S0022-328X(96)06595-3",

language = "English",

volume = "528",

pages = "123--134",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

}

TY - JOUR

T1 - Synthesis, structure and substitution reactions of a heterodimetallic tungsten - manganese complex [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4]

AU - Mays, Martin J.

AU - Owen, Steven M.

AU - Raithby, Paul R.

AU - Reinisch, Paul F.

AU - Shields, Gregory P.

AU - Solan, Gregory A.

N1 - Funding Information: We thank the EPSRC (S.M.O., P.F.R., G.P.S. and G.A.S.) for financial support.

PY - 1997/2/1

Y1 - 1997/2/1

N2 - The room temperature reaction of [(η5-C5H5)W(CO)3(PPh2)] with [Mn(CO)5] in tetrahydrofuran (THF) followed by protonation with H3PO4 gives [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 as the major product. Among the identified minor products from this reaction are [Mn2(CO)9(PPh2H)] 2a, [Mn2(CO)9(PPh2PPh2)] 2b, [Mn2( μ-H)( μ-PPh2)(CO)8] 2c, and [Mn2( μ-PPh2)2(CO)8] 2d. 13CO reacts with complex 1 substituting both the manganese and tungsten carbonyl groups. In contrast, other two-electron donor ligands, L, only substitute the manganese carbonyl groups to give the substituted products [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)3L] (L = P(OMe)3 3a, PMe2Ph 3b, PMePh2 3c, PPh2H 3d), [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2L2] (L = P(OMe)3 4a or PMe2Ph 4b). In the case of the photolytic reaction of 1 with the diphosphine, dppm (dppm = Ph2PCH2PPh2), two products are obtained, one in which the ligand is chelated to the manganese centre, [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2(dppm)] 5, and the other in which the ligand bridges the tungsten manganese centres, [(η5-C5H5)(OC)W( μ-H)( μ-PPh2)( μ-dppm)Mn(CO)3] 6. Conversion of complex 5 to 6 can be achieved by prolonged UV irradiation of 5. A single crystal X-ray diffraction study for [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 is presented.

AB - The room temperature reaction of [(η5-C5H5)W(CO)3(PPh2)] with [Mn(CO)5] in tetrahydrofuran (THF) followed by protonation with H3PO4 gives [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 as the major product. Among the identified minor products from this reaction are [Mn2(CO)9(PPh2H)] 2a, [Mn2(CO)9(PPh2PPh2)] 2b, [Mn2( μ-H)( μ-PPh2)(CO)8] 2c, and [Mn2( μ-PPh2)2(CO)8] 2d. 13CO reacts with complex 1 substituting both the manganese and tungsten carbonyl groups. In contrast, other two-electron donor ligands, L, only substitute the manganese carbonyl groups to give the substituted products [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)3L] (L = P(OMe)3 3a, PMe2Ph 3b, PMePh2 3c, PPh2H 3d), [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2L2] (L = P(OMe)3 4a or PMe2Ph 4b). In the case of the photolytic reaction of 1 with the diphosphine, dppm (dppm = Ph2PCH2PPh2), two products are obtained, one in which the ligand is chelated to the manganese centre, [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)2(dppm)] 5, and the other in which the ligand bridges the tungsten manganese centres, [(η5-C5H5)(OC)W( μ-H)( μ-PPh2)( μ-dppm)Mn(CO)3] 6. Conversion of complex 5 to 6 can be achieved by prolonged UV irradiation of 5. A single crystal X-ray diffraction study for [(η5-C5H5)(OC)2W( μ-H)( μ-PPh2)Mn(CO)4] 1 is presented.

KW - Crystal structure

KW - Heterobimetallics

KW - Hydrido

KW - Manganese

KW - Phosphido

KW - Tungsten

UR - http://www.scopus.com/inward/record.url?scp=0031065876&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(96)06595-3

DO - 10.1016/S0022-328X(96)06595-3

M3 - Article

AN - SCOPUS:0031065876

SN - 0022-328X

VL - 528

SP - 123

EP - 134

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -