The coordination chemistry of iminooxosulphuranes VIII. The coupling of tosyliminooxosulphurane with ethylene, allene, and alkynes coordinated to osmium

Max Herberhold; Anthony F. Hill

doi:10.1016/0022-328X(90)85295-A

The coordination chemistry of iminooxosulphuranes VIII. The coupling of tosyliminooxosulphurane with ethylene, allene, and alkynes coordinated to osmium

Max Herberhold^*
, Anthony F. Hill

^*Corresponding author for this work

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

13 Citations (Scopus)

Abstract

The reactions of the zerovalent osmium nitrosyl complexes [OsCl(NO)(PPh₃)₂(L)] (L CH₂CH₂, CH₂CCH₂, PhCCPh, PhCCH, CH₃CCCH₃ and CF₃CCCF₃) with toluene sulphonyliminooxo-λ⁴-sulphurane, OSNSO₂C₆H₄Me-4 (OSNSO₂R) have been investigated. The ethylene complex reacts either by ethylene substitution to provide [OsCl(NO)(PPh₃)₂(OSNSO₂R)] or by formation of the metallacyclic complex [Os{CH₂CH₂S(NSO₂R)O}Cl(NO)(PPh₃)₂], which has been crystallographically characterised. The allene complex reacts in a similar manner, also forming a metallacycle [Os{C(CH₂)CH₂S(NSO₂R)O}Cl(NO)(PPh₃)₂]. The reactivity of the alkyne complexes depends upon the nature of the alkyne substituents: the strongly bound hexafluorobut-2-yne complex is unreactive, the but-2-yne complex reacts by alkyne substitution (i.e., formation of [OsCl(NO)(PPh₃)₂(OSNSO₂R)]), and the aryl alkyne complexes react by metallacycle formation to give [Os{CPhCR′S(NSO₂R)O}Cl(NO)(PPh₃)₂] (R′ H, Ph). The metallacyclic derivatives are readily and reversibly protonated (HBF₄) at the exocyclic sulphimine substituent.

Original language	English
Pages (from-to)	315-326
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	395
Issue number	3
DOIs	https://doi.org/10.1016/0022-328X(90)85295-A
Publication status	Published - 2 Oct 1990
Externally published	Yes

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@article{63dd347b18ca4446874061a4ae9da39d,

title = "The coordination chemistry of iminooxosulphuranes VIII. The coupling of tosyliminooxosulphurane with ethylene, allene, and alkynes coordinated to osmium",

abstract = "The reactions of the zerovalent osmium nitrosyl complexes [OsCl(NO)(PPh3)2(L)] (L CH2CH2, CH2CCH2, PhCCPh, PhCCH, CH3CCCH3 and CF3CCCF3) with toluene sulphonyliminooxo-λ4-sulphurane, OSNSO2C6H4Me-4 (OSNSO2R) have been investigated. The ethylene complex reacts either by ethylene substitution to provide [OsCl(NO)(PPh3)2(OSNSO2R)] or by formation of the metallacyclic complex [Os\{CH2CH2S(NSO2R)O\}Cl(NO)(PPh3)2], which has been crystallographically characterised. The allene complex reacts in a similar manner, also forming a metallacycle [Os\{C(CH2)CH2S(NSO2R)O\}Cl(NO)(PPh3)2]. The reactivity of the alkyne complexes depends upon the nature of the alkyne substituents: the strongly bound hexafluorobut-2-yne complex is unreactive, the but-2-yne complex reacts by alkyne substitution (i.e., formation of [OsCl(NO)(PPh3)2(OSNSO2R)]), and the aryl alkyne complexes react by metallacycle formation to give [Os\{CPhCR′S(NSO2R)O\}Cl(NO)(PPh3)2] (R′ H, Ph). The metallacyclic derivatives are readily and reversibly protonated (HBF4) at the exocyclic sulphimine substituent.",

author = "Max Herberhold and Hill, \{Anthony F.\}",

year = "1990",

month = oct,

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doi = "10.1016/0022-328X(90)85295-A",

language = "English",

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pages = "315--326",

journal = "Journal of Organometallic Chemistry",

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publisher = "Elsevier B.V.",

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T1 - The coordination chemistry of iminooxosulphuranes VIII. The coupling of tosyliminooxosulphurane with ethylene, allene, and alkynes coordinated to osmium

AU - Herberhold, Max

AU - Hill, Anthony F.

PY - 1990/10/2

Y1 - 1990/10/2

N2 - The reactions of the zerovalent osmium nitrosyl complexes [OsCl(NO)(PPh3)2(L)] (L CH2CH2, CH2CCH2, PhCCPh, PhCCH, CH3CCCH3 and CF3CCCF3) with toluene sulphonyliminooxo-λ4-sulphurane, OSNSO2C6H4Me-4 (OSNSO2R) have been investigated. The ethylene complex reacts either by ethylene substitution to provide [OsCl(NO)(PPh3)2(OSNSO2R)] or by formation of the metallacyclic complex [Os{CH2CH2S(NSO2R)O}Cl(NO)(PPh3)2], which has been crystallographically characterised. The allene complex reacts in a similar manner, also forming a metallacycle [Os{C(CH2)CH2S(NSO2R)O}Cl(NO)(PPh3)2]. The reactivity of the alkyne complexes depends upon the nature of the alkyne substituents: the strongly bound hexafluorobut-2-yne complex is unreactive, the but-2-yne complex reacts by alkyne substitution (i.e., formation of [OsCl(NO)(PPh3)2(OSNSO2R)]), and the aryl alkyne complexes react by metallacycle formation to give [Os{CPhCR′S(NSO2R)O}Cl(NO)(PPh3)2] (R′ H, Ph). The metallacyclic derivatives are readily and reversibly protonated (HBF4) at the exocyclic sulphimine substituent.

AB - The reactions of the zerovalent osmium nitrosyl complexes [OsCl(NO)(PPh3)2(L)] (L CH2CH2, CH2CCH2, PhCCPh, PhCCH, CH3CCCH3 and CF3CCCF3) with toluene sulphonyliminooxo-λ4-sulphurane, OSNSO2C6H4Me-4 (OSNSO2R) have been investigated. The ethylene complex reacts either by ethylene substitution to provide [OsCl(NO)(PPh3)2(OSNSO2R)] or by formation of the metallacyclic complex [Os{CH2CH2S(NSO2R)O}Cl(NO)(PPh3)2], which has been crystallographically characterised. The allene complex reacts in a similar manner, also forming a metallacycle [Os{C(CH2)CH2S(NSO2R)O}Cl(NO)(PPh3)2]. The reactivity of the alkyne complexes depends upon the nature of the alkyne substituents: the strongly bound hexafluorobut-2-yne complex is unreactive, the but-2-yne complex reacts by alkyne substitution (i.e., formation of [OsCl(NO)(PPh3)2(OSNSO2R)]), and the aryl alkyne complexes react by metallacycle formation to give [Os{CPhCR′S(NSO2R)O}Cl(NO)(PPh3)2] (R′ H, Ph). The metallacyclic derivatives are readily and reversibly protonated (HBF4) at the exocyclic sulphimine substituent.

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DO - 10.1016/0022-328X(90)85295-A

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SN - 0022-328X

VL - 395

SP - 315

EP - 326

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 3

ER -

The coordination chemistry of iminooxosulphuranes VIII. The coupling of tosyliminooxosulphurane with ethylene, allene, and alkynes coordinated to osmium

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