Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates:: X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]

B Buriez; DJ Cook; KJ Harlow; AF Hill; T Welton; AJP White; DJ Williams; JDET Wilton-Ely

doi:10.1016/S0022-328X(98)01130-9

Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates: X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]

B Buriez, DJ Cook, KJ Harlow, AF Hill, T Welton, AJP White, DJ Williams, JDET Wilton-Ely

Research output: Contribution to journal › Short survey › peer-review

Abstract

The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] (pz=pyrazol-1-yl) with 4-ethynyl toluene provides [RuCl(=C=CHC(6)H(4)Me4)(PPh3){HB(pz)(3)}] (1a) which reacts with [Et2NH2][S2CNEt2] to give the metallacyclic alkenyl complex [Ru{C(=CHC6H4Me-4)SC(NEt2)S}(PPh3) {HB(pz)(3)}] (2). The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] with diphenylpropynol and Ag[PF6] however provides [Ru(=C=C=CPh2)(PPh3)(2){HB(pz)(3)}]PF6 (3) or in the absence of silver salts, the neutral complex [RuCl-(=C=C=CPh2)(PPh3) {HB(pz)(3)}] (4). Both (3) and (4) react with Na[S2CNMe2] to give the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}(PPh3){HB(pz)(3)}] (5). Treatment of [RuHCl(CO)(PPh3)(3)] with diphenylpropynol and Na[S2CNMe2] provides [Ru(CH=CHCPh2OH)(S2CNMe2)(CO)(PPh3)(2)] which reacts with excess diphenylpropynol to give the alkynyl complex [Ru(C=CCPh2OH)(S2CNMe2)(CO)(PPh3)(2)]. Protonation of this complex with HBF4 provides the allenylidene complex [Ru(=C=C=CPh2)(S2CNMe2)(CO)(PPh3)(2)]BF4 (6) which reacts with Na[S2CNMe2] to give a kinetic isomer (7k) and ultimately a structurally characterised thermodynamic isomer of the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}-(S2CNMe2)(CO)(PPh3)] (7t). (C) 1999 Elsevier Science S.A. All rights reserved.

Original language	English
Pages (from-to)	264-267
Number of pages	4
Journal	Journal of Organometallic Chemistry
Volume	578
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(98)01130-9
Publication status	Published - 22 Apr 1999
Externally published	Yes

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10.1016/S0022-328X(98)01130-9

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Buriez, B., Cook, DJ., Harlow, KJ., Hill, AF., Welton, T., White, AJP., Williams, DJ., & Wilton-Ely, JDET. (1999). Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates: X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]. Journal of Organometallic Chemistry, 578(1-2), 264-267. https://doi.org/10.1016/S0022-328X(98)01130-9

@article{595ab81f5d204e408ac7f49a5956bbe0,

title = "Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates:: X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]",

abstract = "The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] (pz=pyrazol-1-yl) with 4-ethynyl toluene provides [RuCl(=C=CHC(6)H(4)Me4)(PPh3){HB(pz)(3)}] (1a) which reacts with [Et2NH2][S2CNEt2] to give the metallacyclic alkenyl complex [Ru{C(=CHC6H4Me-4)SC(NEt2)S}(PPh3) {HB(pz)(3)}] (2). The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] with diphenylpropynol and Ag[PF6] however provides [Ru(=C=C=CPh2)(PPh3)(2){HB(pz)(3)}]PF6 (3) or in the absence of silver salts, the neutral complex [RuCl-(=C=C=CPh2)(PPh3) {HB(pz)(3)}] (4). Both (3) and (4) react with Na[S2CNMe2] to give the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}(PPh3){HB(pz)(3)}] (5). Treatment of [RuHCl(CO)(PPh3)(3)] with diphenylpropynol and Na[S2CNMe2] provides [Ru(CH=CHCPh2OH)(S2CNMe2)(CO)(PPh3)(2)] which reacts with excess diphenylpropynol to give the alkynyl complex [Ru(C=CCPh2OH)(S2CNMe2)(CO)(PPh3)(2)]. Protonation of this complex with HBF4 provides the allenylidene complex [Ru(=C=C=CPh2)(S2CNMe2)(CO)(PPh3)(2)]BF4 (6) which reacts with Na[S2CNMe2] to give a kinetic isomer (7k) and ultimately a structurally characterised thermodynamic isomer of the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}-(S2CNMe2)(CO)(PPh3)] (7t). (C) 1999 Elsevier Science S.A. All rights reserved.",

keywords = "Allenylidene, Dithiocarbamate, Ligand-coupling, Metallacycle, Ruthenium, Vinylidene",

author = "B Buriez and DJ Cook and KJ Harlow and AF Hill and T Welton and AJP White and DJ Williams and JDET Wilton-Ely",

year = "1999",

month = apr,

day = "22",

doi = "10.1016/S0022-328X(98)01130-9",

language = "English",

volume = "578",

pages = "264--267",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

Buriez, B, Cook, DJ, Harlow, KJ, Hill, AF, Welton, T, White, AJP, Williams, DJ & Wilton-Ely, JDET 1999, 'Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates: X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]', Journal of Organometallic Chemistry, vol. 578, no. 1-2, pp. 264-267. https://doi.org/10.1016/S0022-328X(98)01130-9

Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates: X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]. / Buriez, B; Cook, DJ; Harlow, KJ et al.
In: Journal of Organometallic Chemistry, Vol. 578, No. 1-2, 22.04.1999, p. 264-267.

Research output: Contribution to journal › Short survey › peer-review

TY - JOUR

T1 - Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates:

T2 - X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]

AU - Buriez, B

AU - Cook, DJ

AU - Harlow, KJ

AU - Hill, AF

AU - Welton, T

AU - White, AJP

AU - Williams, DJ

AU - Wilton-Ely, JDET

PY - 1999/4/22

Y1 - 1999/4/22

N2 - The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] (pz=pyrazol-1-yl) with 4-ethynyl toluene provides [RuCl(=C=CHC(6)H(4)Me4)(PPh3){HB(pz)(3)}] (1a) which reacts with [Et2NH2][S2CNEt2] to give the metallacyclic alkenyl complex [Ru{C(=CHC6H4Me-4)SC(NEt2)S}(PPh3) {HB(pz)(3)}] (2). The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] with diphenylpropynol and Ag[PF6] however provides [Ru(=C=C=CPh2)(PPh3)(2){HB(pz)(3)}]PF6 (3) or in the absence of silver salts, the neutral complex [RuCl-(=C=C=CPh2)(PPh3) {HB(pz)(3)}] (4). Both (3) and (4) react with Na[S2CNMe2] to give the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}(PPh3){HB(pz)(3)}] (5). Treatment of [RuHCl(CO)(PPh3)(3)] with diphenylpropynol and Na[S2CNMe2] provides [Ru(CH=CHCPh2OH)(S2CNMe2)(CO)(PPh3)(2)] which reacts with excess diphenylpropynol to give the alkynyl complex [Ru(C=CCPh2OH)(S2CNMe2)(CO)(PPh3)(2)]. Protonation of this complex with HBF4 provides the allenylidene complex [Ru(=C=C=CPh2)(S2CNMe2)(CO)(PPh3)(2)]BF4 (6) which reacts with Na[S2CNMe2] to give a kinetic isomer (7k) and ultimately a structurally characterised thermodynamic isomer of the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}-(S2CNMe2)(CO)(PPh3)] (7t). (C) 1999 Elsevier Science S.A. All rights reserved.

AB - The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] (pz=pyrazol-1-yl) with 4-ethynyl toluene provides [RuCl(=C=CHC(6)H(4)Me4)(PPh3){HB(pz)(3)}] (1a) which reacts with [Et2NH2][S2CNEt2] to give the metallacyclic alkenyl complex [Ru{C(=CHC6H4Me-4)SC(NEt2)S}(PPh3) {HB(pz)(3)}] (2). The reaction of [RuCl(PPh3)(2){HB(pz)(3)}] with diphenylpropynol and Ag[PF6] however provides [Ru(=C=C=CPh2)(PPh3)(2){HB(pz)(3)}]PF6 (3) or in the absence of silver salts, the neutral complex [RuCl-(=C=C=CPh2)(PPh3) {HB(pz)(3)}] (4). Both (3) and (4) react with Na[S2CNMe2] to give the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}(PPh3){HB(pz)(3)}] (5). Treatment of [RuHCl(CO)(PPh3)(3)] with diphenylpropynol and Na[S2CNMe2] provides [Ru(CH=CHCPh2OH)(S2CNMe2)(CO)(PPh3)(2)] which reacts with excess diphenylpropynol to give the alkynyl complex [Ru(C=CCPh2OH)(S2CNMe2)(CO)(PPh3)(2)]. Protonation of this complex with HBF4 provides the allenylidene complex [Ru(=C=C=CPh2)(S2CNMe2)(CO)(PPh3)(2)]BF4 (6) which reacts with Na[S2CNMe2] to give a kinetic isomer (7k) and ultimately a structurally characterised thermodynamic isomer of the metallacyclic allenyl complex [Ru{C(=C=CPh2)SC(NMe2)S}-(S2CNMe2)(CO)(PPh3)] (7t). (C) 1999 Elsevier Science S.A. All rights reserved.

KW - Allenylidene

KW - Dithiocarbamate

KW - Ligand-coupling

KW - Metallacycle

KW - Ruthenium

KW - Vinylidene

UR - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=anu_research_portal_plus2&SrcAuth=WosAPI&KeyUT=WOS:000080412600030&DestLinkType=FullRecord&DestApp=WOS_CPL

U2 - 10.1016/S0022-328X(98)01130-9

DO - 10.1016/S0022-328X(98)01130-9

M3 - Short survey

SN - 0022-328X

VL - 578

SP - 264

EP - 267

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Buriez B, Cook DJ, Harlow KJ, Hill AF, Welton T, White AJP et al. Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates: X-ray structure of [Ru{C(=C=CPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]. Journal of Organometallic Chemistry. 1999 Apr 22;578(1-2):264-267. doi: 10.1016/S0022-328X(98)01130-9

Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates: X-ray structure of [Ru{C(=C=CPh<sub>2</sub>)SC(NMe<sub>2</sub>)S}(S<sub>2</sub>CNMe<sub>2</sub>)(CO)(PPh<sub>3</sub>)]

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