The coordination chemistry of iminooxosulphuranes VII. Coordinative activation of tolyliminooxosulphurane towards electrophiles

Max Herberhold; Anthony F. Hill

doi:10.1016/0022-328X(90)85278-7

The coordination chemistry of iminooxosulphuranes VII. Coordinative activation of tolyliminooxosulphurane towards electrophiles

Max Herberhold^*, Anthony F. Hill

^*Corresponding author for this work

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

8 Citations (Scopus)

Abstract

The reactions of the p-tolyliminooxosulphurane complexes [Ru(CO)(L)(PPh₃)₂ (OSNR)] (L=CO, CNC₆H₃Me-2,6, CN^tBu; R=C₆H₄Me-4 (p-tolyl)) and [OsCl(NO)(PPh₃)₂(OSNR)] with a range of electrophiles have been investigated: [Ru(CO)(CNC₆H₃Me₂-2,6)(PPh₃)₂(OSNR)] reacts with hexafluoroantimonic acid to give the N-protonated salt [Ru(OSNHR)(CO)(CNC₆H₃Me₂-2,6)(PPh₃)₂]SbF₆, which in turn reacts with nucleophilic ligands CN^tBu and SCN^- to give the η¹-sulphinamido complexes [Ru(OSNHR)(CO)(CN^tBu)(CNC₆H₃Me₂-2,6)(PPh₃)₂]⁺ and [Ru(OSNHR)(SCN)(CO)(CNC₆H₃Me₂-2,6)(PPh₃)₂]. Alkylation of [Ru(CO)(L)(PPh₃)₂(OSNR)] with R′X occurs at oxygen, giving the complexes [Ru(R′OSNR)(CO)(L)(PPh₃)₂]X (L=CNC₆H₃Me₂-2,6, R′=CH₃, X=CF₃SO₃; R′=C₂H₅, X=SO₃F; L=CO, R′=CH₃, X=CF₃SO₃). Silylation of [Ru(CO)(CNC₆H₃Me₂-2,6)(PPh₃)₂(OSNR)] with Me₃SiOSO₂CF₃ occurs at oxygen, to give [Ru(Me₃SiOSNR)(CO)(CNC₆H₃Me₂-2,6)(PPh₃)₂]O₃SCF₃ whilst [OsCl(NO)(PPh₃)₂(OSNR)] with BF₃OEt₂ gives [OsCl(NO)(PPh₃)₂(F₃BOSNR)]. The adducts formed by reactions of coordinated iminooxosulphuranes with HSbF₆, Me₃SiOSO₂CF₃ and BF₃OEt₂ reacted with KOH/MeOH, CsF and acetone, respectively to regenerate the zerovalent iminooxosulphurane complexes, but alkylation was found to be irreversible.

Original language	English
Pages (from-to)	207-218
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	395
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(90)85278-7
Publication status	Published - 25 Sept 1990
Externally published	Yes

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10.1016/0022-328X(90)85278-7

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@article{23f49a47876d489d90b9ff8bd03697fc,

title = "The coordination chemistry of iminooxosulphuranes VII. Coordinative activation of tolyliminooxosulphurane towards electrophiles",

abstract = "The reactions of the p-tolyliminooxosulphurane complexes [Ru(CO)(L)(PPh3)2 (OSNR)] (L=CO, CNC6H3Me-2,6, CNtBu; R=C6H4Me-4 (p-tolyl)) and [OsCl(NO)(PPh3)2(OSNR)] with a range of electrophiles have been investigated: [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] reacts with hexafluoroantimonic acid to give the N-protonated salt [Ru(OSNHR)(CO)(CNC6H3Me2-2,6)(PPh3)2]SbF6, which in turn reacts with nucleophilic ligands CNtBu and SCN- to give the η1-sulphinamido complexes [Ru(OSNHR)(CO)(CNtBu)(CNC6H3Me2-2,6)(PPh3)2]+ and [Ru(OSNHR)(SCN)(CO)(CNC6H3Me2-2,6)(PPh3)2]. Alkylation of [Ru(CO)(L)(PPh3)2(OSNR)] with R′X occurs at oxygen, giving the complexes [Ru(R′OSNR)(CO)(L)(PPh3)2]X (L=CNC6H3Me2-2,6, R′=CH3, X=CF3SO3; R′=C2H5, X=SO3F; L=CO, R′=CH3, X=CF3SO3). Silylation of [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] with Me3SiOSO2CF3 occurs at oxygen, to give [Ru(Me3SiOSNR)(CO)(CNC6H3Me2-2,6)(PPh3)2]O3SCF3 whilst [OsCl(NO)(PPh3)2(OSNR)] with BF3OEt2 gives [OsCl(NO)(PPh3)2(F3BOSNR)]. The adducts formed by reactions of coordinated iminooxosulphuranes with HSbF6, Me3SiOSO2CF3 and BF3OEt2 reacted with KOH/MeOH, CsF and acetone, respectively to regenerate the zerovalent iminooxosulphurane complexes, but alkylation was found to be irreversible.",

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

year = "1990",

month = sep,

day = "25",

doi = "10.1016/0022-328X(90)85278-7",

language = "English",

volume = "395",

pages = "207--218",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "2",

}

TY - JOUR

T1 - The coordination chemistry of iminooxosulphuranes VII. Coordinative activation of tolyliminooxosulphurane towards electrophiles

AU - Herberhold, Max

AU - Hill, Anthony F.

PY - 1990/9/25

Y1 - 1990/9/25

N2 - The reactions of the p-tolyliminooxosulphurane complexes [Ru(CO)(L)(PPh3)2 (OSNR)] (L=CO, CNC6H3Me-2,6, CNtBu; R=C6H4Me-4 (p-tolyl)) and [OsCl(NO)(PPh3)2(OSNR)] with a range of electrophiles have been investigated: [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] reacts with hexafluoroantimonic acid to give the N-protonated salt [Ru(OSNHR)(CO)(CNC6H3Me2-2,6)(PPh3)2]SbF6, which in turn reacts with nucleophilic ligands CNtBu and SCN- to give the η1-sulphinamido complexes [Ru(OSNHR)(CO)(CNtBu)(CNC6H3Me2-2,6)(PPh3)2]+ and [Ru(OSNHR)(SCN)(CO)(CNC6H3Me2-2,6)(PPh3)2]. Alkylation of [Ru(CO)(L)(PPh3)2(OSNR)] with R′X occurs at oxygen, giving the complexes [Ru(R′OSNR)(CO)(L)(PPh3)2]X (L=CNC6H3Me2-2,6, R′=CH3, X=CF3SO3; R′=C2H5, X=SO3F; L=CO, R′=CH3, X=CF3SO3). Silylation of [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] with Me3SiOSO2CF3 occurs at oxygen, to give [Ru(Me3SiOSNR)(CO)(CNC6H3Me2-2,6)(PPh3)2]O3SCF3 whilst [OsCl(NO)(PPh3)2(OSNR)] with BF3OEt2 gives [OsCl(NO)(PPh3)2(F3BOSNR)]. The adducts formed by reactions of coordinated iminooxosulphuranes with HSbF6, Me3SiOSO2CF3 and BF3OEt2 reacted with KOH/MeOH, CsF and acetone, respectively to regenerate the zerovalent iminooxosulphurane complexes, but alkylation was found to be irreversible.

AB - The reactions of the p-tolyliminooxosulphurane complexes [Ru(CO)(L)(PPh3)2 (OSNR)] (L=CO, CNC6H3Me-2,6, CNtBu; R=C6H4Me-4 (p-tolyl)) and [OsCl(NO)(PPh3)2(OSNR)] with a range of electrophiles have been investigated: [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] reacts with hexafluoroantimonic acid to give the N-protonated salt [Ru(OSNHR)(CO)(CNC6H3Me2-2,6)(PPh3)2]SbF6, which in turn reacts with nucleophilic ligands CNtBu and SCN- to give the η1-sulphinamido complexes [Ru(OSNHR)(CO)(CNtBu)(CNC6H3Me2-2,6)(PPh3)2]+ and [Ru(OSNHR)(SCN)(CO)(CNC6H3Me2-2,6)(PPh3)2]. Alkylation of [Ru(CO)(L)(PPh3)2(OSNR)] with R′X occurs at oxygen, giving the complexes [Ru(R′OSNR)(CO)(L)(PPh3)2]X (L=CNC6H3Me2-2,6, R′=CH3, X=CF3SO3; R′=C2H5, X=SO3F; L=CO, R′=CH3, X=CF3SO3). Silylation of [Ru(CO)(CNC6H3Me2-2,6)(PPh3)2(OSNR)] with Me3SiOSO2CF3 occurs at oxygen, to give [Ru(Me3SiOSNR)(CO)(CNC6H3Me2-2,6)(PPh3)2]O3SCF3 whilst [OsCl(NO)(PPh3)2(OSNR)] with BF3OEt2 gives [OsCl(NO)(PPh3)2(F3BOSNR)]. The adducts formed by reactions of coordinated iminooxosulphuranes with HSbF6, Me3SiOSO2CF3 and BF3OEt2 reacted with KOH/MeOH, CsF and acetone, respectively to regenerate the zerovalent iminooxosulphurane complexes, but alkylation was found to be irreversible.

UR - https://www.scopus.com/pages/publications/44949289826

UR - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=anu_research_portal_plus2&SrcAuth=WosAPI&KeyUT=WOS:A1990EA97400006&DestLinkType=FullRecord&DestApp=WOS_CPL

U2 - 10.1016/0022-328X(90)85278-7

DO - 10.1016/0022-328X(90)85278-7

M3 - Article

AN - SCOPUS:44949289826

SN - 0022-328X

VL - 395

SP - 207

EP - 218

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -

The coordination chemistry of iminooxosulphuranes VII. Coordinative activation of tolyliminooxosulphurane towards electrophiles

Abstract

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