Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl2(co)(Ple3)2] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands

Andreas Mayr; Marianna F. Asaro; Michael A. Kjelsberg; Ken S. Lee; Donna Van Engen

doi:10.1021/om00145a036

Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl₂(co)(Ple₃)₂] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands

Andreas Mayr
, Marianna F. Asaro
, Michael A. Kjelsberg
, Ken S. Lee
, Donna Van Engen

Chemistry

Princeton University

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

55 Scopus citations

Abstract

Efficient procedures for the synthesis of the tungsten carbyne complexes [(W≡CR)CI(CO)(PMe₃)₃] (2, R = C₆H_5,C₆H₄CH₃-4) and [(M≡CPh)Br(PMe₃)₄] (3, M = W. and 5. M = Mo) are described. Reaction of complex 3 with HBr gives the hydrido complex [(W≡CPh)Br₂(H)-(PMe₃)₃]. Reaction of complexes 2 with HCI gives the tungsten alkylidene complexes [(W≡CHR)CI₂(CO)-(PMe₃)₂] (7) that can be deprotonated to give coordinatively labile anionic tungsten carbyne complexes [(W≡CR)CI₂(CO(PMe₃)₂]^-. Dehydrochlorination of 7 in the presence of ligands provides substituted tungsten carbyne complexes [(W≡CR)CI(COXPMe₃)₂L] (L = pyridine, P-(OMe)₃, CNCMe₃). The crystal structure of the benzylidene complex [(W≡CHPh)CI₂(CO)(PMe₃)₂] is reported.

Original language	English
Pages (from-to)	432-434
Number of pages	3
Journal	Organometallics
Volume	6
Issue number	2
DOIs	https://doi.org/10.1021/om00145a036
State	Published - Feb 1 1987

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Mayr, A., Asaro, M. F., Kjelsberg, M. A., Lee, K. S., & Engen, D. V. (1987). Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl₂(co)(Ple₃)₂] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands. Organometallics, 6(2), 432-434. https://doi.org/10.1021/om00145a036

Mayr, Andreas ; Asaro, Marianna F. ; Kjelsberg, Michael A. et al. / Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl₂(co)(Ple₃)₂] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands. In: Organometallics. 1987 ; Vol. 6, No. 2. pp. 432-434.

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title = "Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl2(co)(Ple3)2] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands",

abstract = "Efficient procedures for the synthesis of the tungsten carbyne complexes [(W≡CR)CI(CO)(PMe3)3] (2, R = C6H5,C6H4CH3-4) and [(M≡CPh)Br(PMe3)4] (3, M = W. and 5. M = Mo) are described. Reaction of complex 3 with HBr gives the hydrido complex [(W≡CPh)Br2(H)-(PMe3)3]. Reaction of complexes 2 with HCI gives the tungsten alkylidene complexes [(W≡CHR)CI2(CO)-(PMe3)2] (7) that can be deprotonated to give coordinatively labile anionic tungsten carbyne complexes [(W≡CR)CI2(CO(PMe3)2]-. Dehydrochlorination of 7 in the presence of ligands provides substituted tungsten carbyne complexes [(W≡CR)CI(COXPMe3)2L] (L = pyridine, P-(OMe)3, CNCMe3). The crystal structure of the benzylidene complex [(W≡CHPh)CI2(CO)(PMe3)2] is reported.",

author = "Andreas Mayr and Asaro, \{Marianna F.\} and Kjelsberg, \{Michael A.\} and Lee, \{Ken S.\} and Engen, \{Donna Van\}",

year = "1987",

month = feb,

day = "1",

doi = "10.1021/om00145a036",

language = "English",

volume = "6",

pages = "432--434",

journal = "Organometallics",

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Mayr, A, Asaro, MF, Kjelsberg, MA, Lee, KS & Engen, DV 1987, 'Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl₂(co)(Ple₃)₂] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands', Organometallics, vol. 6, no. 2, pp. 432-434. https://doi.org/10.1021/om00145a036

Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl₂(co)(Ple₃)₂] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands. / Mayr, Andreas; Asaro, Marianna F.; Kjelsberg, Michael A. et al.
In: Organometallics, Vol. 6, No. 2, 01.02.1987, p. 432-434.

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

TY - JOUR

T1 - Synthesis and Protonation Reactions of Trimethylphosphine-Substituted Carbyne Complexes of Molybdenum and Tungsten. The Tungsten Alkylldene Complexes [(W=CHR)Cl2(co)(Ple3)2] as Precursors for Carbyne Complexes Containing Weakly Coordinated Ligands

AU - Mayr, Andreas

AU - Asaro, Marianna F.

AU - Kjelsberg, Michael A.

AU - Lee, Ken S.

AU - Engen, Donna Van

PY - 1987/2/1

Y1 - 1987/2/1

N2 - Efficient procedures for the synthesis of the tungsten carbyne complexes [(W≡CR)CI(CO)(PMe3)3] (2, R = C6H5,C6H4CH3-4) and [(M≡CPh)Br(PMe3)4] (3, M = W. and 5. M = Mo) are described. Reaction of complex 3 with HBr gives the hydrido complex [(W≡CPh)Br2(H)-(PMe3)3]. Reaction of complexes 2 with HCI gives the tungsten alkylidene complexes [(W≡CHR)CI2(CO)-(PMe3)2] (7) that can be deprotonated to give coordinatively labile anionic tungsten carbyne complexes [(W≡CR)CI2(CO(PMe3)2]-. Dehydrochlorination of 7 in the presence of ligands provides substituted tungsten carbyne complexes [(W≡CR)CI(COXPMe3)2L] (L = pyridine, P-(OMe)3, CNCMe3). The crystal structure of the benzylidene complex [(W≡CHPh)CI2(CO)(PMe3)2] is reported.

AB - Efficient procedures for the synthesis of the tungsten carbyne complexes [(W≡CR)CI(CO)(PMe3)3] (2, R = C6H5,C6H4CH3-4) and [(M≡CPh)Br(PMe3)4] (3, M = W. and 5. M = Mo) are described. Reaction of complex 3 with HBr gives the hydrido complex [(W≡CPh)Br2(H)-(PMe3)3]. Reaction of complexes 2 with HCI gives the tungsten alkylidene complexes [(W≡CHR)CI2(CO)-(PMe3)2] (7) that can be deprotonated to give coordinatively labile anionic tungsten carbyne complexes [(W≡CR)CI2(CO(PMe3)2]-. Dehydrochlorination of 7 in the presence of ligands provides substituted tungsten carbyne complexes [(W≡CR)CI(COXPMe3)2L] (L = pyridine, P-(OMe)3, CNCMe3). The crystal structure of the benzylidene complex [(W≡CHPh)CI2(CO)(PMe3)2] is reported.

UR - https://www.scopus.com/pages/publications/0000942493

U2 - 10.1021/om00145a036

DO - 10.1021/om00145a036

M3 - Article

AN - SCOPUS:0000942493

SN - 0276-7333

VL - 6

SP - 432

EP - 434

JO - Organometallics

JF - Organometallics

IS - 2