Synthesis and structure of W(η2-mp)2(CO)3 (mp = monoanion of 2-mercaptopyridine) and its reactions with 2,2′-pyridine disulfide and/or NO to yield W(η2-mp)4, W(η2-mp)2(NO)2, and W(η2-mp)3(NO)

K. Sukcharoenphon; K. B. Capps; K. A. Abboud; C. D. Hoff

doi:10.1021/ic000722r

Synthesis and structure of W(η²-mp)₂(CO)₃ (mp = monoanion of 2-mercaptopyridine) and its reactions with 2,2′-pyridine disulfide and/or NO to yield W(η²-mp)₄, W(η²-mp)₂(NO)₂, and W(η²-mp)₃(NO)

K. Sukcharoenphon, K. B. Capps, K. A. Abboud, C. D. Hoff

Chemistry

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

15 Scopus citations

Abstract

Oxidative addition of the sulfur-sulfur bond of 2,2′-pyridine disulfide (C₅H₄NS-SC₅H₄N) with L₃W(CO)₃ [L = pyridine, 1/3 CHPT; CHPT = cycloheptatriene] in methylene chloride solution yields the seven-coordinate W(II) thiolate complex W(η²-mp)₂(CO)₃ (mp = monoanion of 2-mercaptopyridine). This complex undergoes slow further oxidative addition with additional pyridine disulfide, yielding W(η²-mp)₄. Reaction of W(η²-mp)₂(CO)₃ with NO results in quantitative formation of the six-coordinate W(O) complex W(η²-mp)₂(NO)₂. Reaction of W(η²-mp)₂(CO)₃ with NO in the presence of added pyridine disulfide yields the seven-coordinate W(II) nitrosyl complex W(η²-mp)₃(NO) as well as W(η²-mp)₂(NO)₂ and trace amounts of W(η²-mp)₄. The complex W(η²-mp)₃(NO) is formed during the course of the reaction and not by reaction of W(η²-mp)₄ or W(η²-mp)₂(NO)² with NO under these conditions. The crystal structures of W(η²- mp)₂(CO)₃, W(η²-mp)₂(NO)², and W(η²-mp)₃(NO) are reported.

Original language	English (US)
Pages (from-to)	2402-2408
Number of pages	7
Journal	Inorganic Chemistry
Volume	40
Issue number	10
DOIs	https://doi.org/10.1021/ic000722r
State	Published - May 7 2001

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Synthesis and structure of W(η²-mp)₂(CO)₃ (mp = monoanion of 2-mercaptopyridine) and its reactions with 2,2′-pyridine disulfide and/or NO to yield W(η²-mp)₄, W(η²-mp)₂(NO)₂, and W(η²-mp)₃(NO). / Sukcharoenphon, K.; Capps, K. B.; Abboud, K. A.; Hoff, C. D.

In: Inorganic Chemistry, Vol. 40, No. 10, 07.05.2001, p. 2402-2408.

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

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title = "Synthesis and structure of W(η2-mp)2(CO)3 (mp = monoanion of 2-mercaptopyridine) and its reactions with 2,2′-pyridine disulfide and/or NO to yield W(η2-mp)4, W(η2-mp)2(NO)2, and W(η2-mp)3(NO)",

abstract = "Oxidative addition of the sulfur-sulfur bond of 2,2′-pyridine disulfide (C5H4NS-SC5H4N) with L3W(CO)3 [L = pyridine, 1/3 CHPT; CHPT = cycloheptatriene] in methylene chloride solution yields the seven-coordinate W(II) thiolate complex W(η2-mp)2(CO)3 (mp = monoanion of 2-mercaptopyridine). This complex undergoes slow further oxidative addition with additional pyridine disulfide, yielding W(η2-mp)4. Reaction of W(η2-mp)2(CO)3 with NO results in quantitative formation of the six-coordinate W(O) complex W(η2-mp)2(NO)2. Reaction of W(η2-mp)2(CO)3 with NO in the presence of added pyridine disulfide yields the seven-coordinate W(II) nitrosyl complex W(η2-mp)3(NO) as well as W(η2-mp)2(NO)2 and trace amounts of W(η2-mp)4. The complex W(η2-mp)3(NO) is formed during the course of the reaction and not by reaction of W(η2-mp)4 or W(η2-mp)2(NO)2 with NO under these conditions. The crystal structures of W(η2- mp)2(CO)3, W(η2-mp)2(NO)2, and W(η2-mp)3(NO) are reported.",

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AU - Sukcharoenphon, K.

AU - Capps, K. B.

AU - Abboud, K. A.

AU - Hoff, C. D.

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N2 - Oxidative addition of the sulfur-sulfur bond of 2,2′-pyridine disulfide (C5H4NS-SC5H4N) with L3W(CO)3 [L = pyridine, 1/3 CHPT; CHPT = cycloheptatriene] in methylene chloride solution yields the seven-coordinate W(II) thiolate complex W(η2-mp)2(CO)3 (mp = monoanion of 2-mercaptopyridine). This complex undergoes slow further oxidative addition with additional pyridine disulfide, yielding W(η2-mp)4. Reaction of W(η2-mp)2(CO)3 with NO results in quantitative formation of the six-coordinate W(O) complex W(η2-mp)2(NO)2. Reaction of W(η2-mp)2(CO)3 with NO in the presence of added pyridine disulfide yields the seven-coordinate W(II) nitrosyl complex W(η2-mp)3(NO) as well as W(η2-mp)2(NO)2 and trace amounts of W(η2-mp)4. The complex W(η2-mp)3(NO) is formed during the course of the reaction and not by reaction of W(η2-mp)4 or W(η2-mp)2(NO)2 with NO under these conditions. The crystal structures of W(η2- mp)2(CO)3, W(η2-mp)2(NO)2, and W(η2-mp)3(NO) are reported.

AB - Oxidative addition of the sulfur-sulfur bond of 2,2′-pyridine disulfide (C5H4NS-SC5H4N) with L3W(CO)3 [L = pyridine, 1/3 CHPT; CHPT = cycloheptatriene] in methylene chloride solution yields the seven-coordinate W(II) thiolate complex W(η2-mp)2(CO)3 (mp = monoanion of 2-mercaptopyridine). This complex undergoes slow further oxidative addition with additional pyridine disulfide, yielding W(η2-mp)4. Reaction of W(η2-mp)2(CO)3 with NO results in quantitative formation of the six-coordinate W(O) complex W(η2-mp)2(NO)2. Reaction of W(η2-mp)2(CO)3 with NO in the presence of added pyridine disulfide yields the seven-coordinate W(II) nitrosyl complex W(η2-mp)3(NO) as well as W(η2-mp)2(NO)2 and trace amounts of W(η2-mp)4. The complex W(η2-mp)3(NO) is formed during the course of the reaction and not by reaction of W(η2-mp)4 or W(η2-mp)2(NO)2 with NO under these conditions. The crystal structures of W(η2- mp)2(CO)3, W(η2-mp)2(NO)2, and W(η2-mp)3(NO) are reported.

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