Bimetallic complexes with bridging dithiaalkane ligands: Preparation and kinetic study

Khalil J. Asali; Mohammad El-Khateeb; Musa M. Musa

doi:10.1080/0095897021000025534

Bimetallic complexes with bridging dithiaalkane ligands: Preparation and kinetic study

Khalil J. Asali^*, Mohammad El-Khateeb, Musa M. Musa

^*Corresponding author for this work

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

8 Scopus citations

Abstract

Reactions of M(CO)₅THF, which was generated photochemically from M(CO)₆ in THF, with (CH³)₃CS(CH₂)_nSC (CH₃)₃ (=SS; n=5, 6; M=W, Cr) at room temperature afforded exclusively the bimetallic complexes (CO)₅MSSM(CO)₅. These new complexes with dithiaalkane bridging ligands have been characterized by IR and H NMR spectroscopies and elemental analysis. Kinetic studies of ligand-exchange reactions in these complexes in chlorobenzene (= CB) solutions employing tri(iso-propyl)phosphite (= L) as an incoming nucleophile indicated that the bridging ligand SS is replaced by L to afford finally (CO)₅MP(O-i-Pr)₃ as the sole reaction product. The kinetic data have also confirmed that replacement of SS by L under pseudo-first-order reaction conditions is dissociative and proceeds via a mechanism which involves initial M-S bond breaking followed by other steps. First order rate constants and activation parameters for these reactions have been determined.

Original language	English
Pages (from-to)	1199-1207
Number of pages	9
Journal	Journal of Coordination Chemistry
Volume	55
Issue number	10
DOIs	https://doi.org/10.1080/0095897021000025534
State	Published - Oct 2002
Externally published	Yes

Bibliographical note

Funding Information:
We thank the Deanship of Research, Jordan University of Science and Technology for financial support, Grant No. 59/98.

Keywords

Bimetallic
Kinetics
Mechanism
Metal carbonyls
Substitution
Sulfur bridging ligands

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Materials Chemistry

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10.1080/0095897021000025534

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title = "Bimetallic complexes with bridging dithiaalkane ligands: Preparation and kinetic study",

abstract = "Reactions of M(CO)5THF, which was generated photochemically from M(CO)6 in THF, with (CH3)3CS(CH2)nSC (CH3)3 (=SS; n=5, 6; M=W, Cr) at room temperature afforded exclusively the bimetallic complexes (CO)5MSSM(CO)5. These new complexes with dithiaalkane bridging ligands have been characterized by IR and H NMR spectroscopies and elemental analysis. Kinetic studies of ligand-exchange reactions in these complexes in chlorobenzene (= CB) solutions employing tri(iso-propyl)phosphite (= L) as an incoming nucleophile indicated that the bridging ligand SS is replaced by L to afford finally (CO)5MP(O-i-Pr)3 as the sole reaction product. The kinetic data have also confirmed that replacement of SS by L under pseudo-first-order reaction conditions is dissociative and proceeds via a mechanism which involves initial M-S bond breaking followed by other steps. First order rate constants and activation parameters for these reactions have been determined.",

keywords = "Bimetallic, Kinetics, Mechanism, Metal carbonyls, Substitution, Sulfur bridging ligands",

author = "Asali, {Khalil J.} and Mohammad El-Khateeb and Musa, {Musa M.}",

note = "Funding Information: We thank the Deanship of Research, Jordan University of Science and Technology for financial support, Grant No. 59/98.",

year = "2002",

month = oct,

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language = "English",

volume = "55",

pages = "1199--1207",

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T1 - Bimetallic complexes with bridging dithiaalkane ligands

T2 - Preparation and kinetic study

AU - Asali, Khalil J.

AU - El-Khateeb, Mohammad

AU - Musa, Musa M.

N1 - Funding Information: We thank the Deanship of Research, Jordan University of Science and Technology for financial support, Grant No. 59/98.

PY - 2002/10

Y1 - 2002/10

N2 - Reactions of M(CO)5THF, which was generated photochemically from M(CO)6 in THF, with (CH3)3CS(CH2)nSC (CH3)3 (=SS; n=5, 6; M=W, Cr) at room temperature afforded exclusively the bimetallic complexes (CO)5MSSM(CO)5. These new complexes with dithiaalkane bridging ligands have been characterized by IR and H NMR spectroscopies and elemental analysis. Kinetic studies of ligand-exchange reactions in these complexes in chlorobenzene (= CB) solutions employing tri(iso-propyl)phosphite (= L) as an incoming nucleophile indicated that the bridging ligand SS is replaced by L to afford finally (CO)5MP(O-i-Pr)3 as the sole reaction product. The kinetic data have also confirmed that replacement of SS by L under pseudo-first-order reaction conditions is dissociative and proceeds via a mechanism which involves initial M-S bond breaking followed by other steps. First order rate constants and activation parameters for these reactions have been determined.

AB - Reactions of M(CO)5THF, which was generated photochemically from M(CO)6 in THF, with (CH3)3CS(CH2)nSC (CH3)3 (=SS; n=5, 6; M=W, Cr) at room temperature afforded exclusively the bimetallic complexes (CO)5MSSM(CO)5. These new complexes with dithiaalkane bridging ligands have been characterized by IR and H NMR spectroscopies and elemental analysis. Kinetic studies of ligand-exchange reactions in these complexes in chlorobenzene (= CB) solutions employing tri(iso-propyl)phosphite (= L) as an incoming nucleophile indicated that the bridging ligand SS is replaced by L to afford finally (CO)5MP(O-i-Pr)3 as the sole reaction product. The kinetic data have also confirmed that replacement of SS by L under pseudo-first-order reaction conditions is dissociative and proceeds via a mechanism which involves initial M-S bond breaking followed by other steps. First order rate constants and activation parameters for these reactions have been determined.

KW - Bimetallic

KW - Kinetics

KW - Mechanism

KW - Metal carbonyls

KW - Substitution

KW - Sulfur bridging ligands

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DO - 10.1080/0095897021000025534

M3 - Article

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JO - Journal of Coordination Chemistry

JF - Journal of Coordination Chemistry

IS - 10

ER -

Bimetallic complexes with bridging dithiaalkane ligands: Preparation and kinetic study

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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