Bis(acetylacetonato)ruthenium(ii) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac) 2(Ph2PCCR)2] (R = H, Me, Ph) complexes and the binuclear complex cis-[{Ru(acac)2}2(-Ph 2PCCPPh2)}2]

Martin A. Bennett; Matthew J. Byrnes; Anthony C. Willis

doi:10.1039/b618365d

Bis(acetylacetonato)ruthenium(ii) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac) ₂(Ph₂PCCR)₂] (R = H, Me, Ph) complexes and the binuclear complex cis-[{Ru(acac)₂}₂(-Ph ₂PCCPPh₂)}₂]

Martin A. Bennett^*, Matthew J. Byrnes, Anthony C. Willis

^*Corresponding author for this work

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

16 Citations (Scopus)

Abstract

Two equivalents of Ph₂PCCR (R = H, Me, Ph) react with thf solutions of cis-[Ru(acac)₂(η²-alkene)₂] (acac = acetylacetonato; alkene = C₂H₄, 1; C ₈H₁₄, 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac)₂(Ph₂PCCR) ₂] (R = H, trans-3; Me = trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac)₂(Ph₂PCCR) ₂] (R = Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph₂PCCPPh₂ with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac)₂(-Ph₂PCCPPh₂)]_n (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac)₂(-Ph₂PCCPPh ₂)}₂] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac) ₂L₂] (L = PPh₃, PPh₂Me). Electrochemical studies of cis-6 show two reversible Ru^II/III oxidation processes separated by 300 mV, the estimated comproportionation constant (K_c) for the equilibrium cis-6²⁺ + cis-6 2(cis-6⁺) being ca. 10⁵. However, UV-Vis spectra of cis-6⁺ and cis-6²⁺, generated electrochemically at -50 °C, indicate that cis-6⁺ is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF₆ to trans-3 and trans-4 forms the green air-stable complexes trans-3·PF₆ and trans-4·PF₆, respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4·PF₆ and cis-6 have been confirmed by X-ray crystallography.

Original language	English
Pages (from-to)	1677-1686
Number of pages	10
Journal	Dalton Transactions
Issue number	17
DOIs	https://doi.org/10.1039/b618365d
Publication status	Published - 2007

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@article{d93cde959a3348408ea68b758ff76728,

title = "Bis(acetylacetonato)ruthenium(ii) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac) 2(Ph2PCCR)2] (R = H, Me, Ph) complexes and the binuclear complex cis-[\{Ru(acac)2\}2(-Ph 2PCCPPh2)\}2]",

abstract = "Two equivalents of Ph2PCCR (R = H, Me, Ph) react with thf solutions of cis-[Ru(acac)2(η2-alkene)2] (acac = acetylacetonato; alkene = C2H4, 1; C 8H14, 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac)2(Ph2PCCR) 2] (R = H, trans-3; Me = trans-4; Ph, trans-5) in isolated yields of 60-98\%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac)2(Ph2PCCR) 2] (R = Me, cis-4; Ph, cis-5), isolated in yields of ca. 65\%. From the reaction of two equivalents of Ph2PCCPPh2 with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac)2(-Ph2PCCPPh2)]n (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[\{Ru(acac)2(-Ph2PCCPPh 2)\}2] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac) 2L2] (L = PPh3, PPh2Me). Electrochemical studies of cis-6 show two reversible RuII/III oxidation processes separated by 300 mV, the estimated comproportionation constant (Kc) for the equilibrium cis-62+ + cis-6 2(cis-6+) being ca. 105. However, UV-Vis spectra of cis-6+ and cis-62+, generated electrochemically at -50 °C, indicate that cis-6+ is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF6 to trans-3 and trans-4 forms the green air-stable complexes trans-3·PF6 and trans-4·PF6, respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4·PF6 and cis-6 have been confirmed by X-ray crystallography.",

author = "Bennett, \{Martin A.\} and Byrnes, \{Matthew J.\} and Willis, \{Anthony C.\}",

year = "2007",

doi = "10.1039/b618365d",

language = "English",

pages = "1677--1686",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "17",

}

Bis(acetylacetonato)ruthenium(ii) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac) ₂(Ph₂PCCR)₂] (R = H, Me, Ph) complexes and the binuclear complex cis-[{Ru(acac)₂}₂(-Ph ₂PCCPPh₂)}₂]. / Bennett, Martin A.; Byrnes, Matthew J.; Willis, Anthony C.
In: Dalton Transactions, No. 17, 2007, p. 1677-1686.

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

TY - JOUR

T1 - Bis(acetylacetonato)ruthenium(ii) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac) 2(Ph2PCCR)2] (R = H, Me, Ph) complexes and the binuclear complex cis-[{Ru(acac)2}2(-Ph 2PCCPPh2)}2]

AU - Bennett, Martin A.

AU - Byrnes, Matthew J.

AU - Willis, Anthony C.

PY - 2007

Y1 - 2007

N2 - Two equivalents of Ph2PCCR (R = H, Me, Ph) react with thf solutions of cis-[Ru(acac)2(η2-alkene)2] (acac = acetylacetonato; alkene = C2H4, 1; C 8H14, 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac)2(Ph2PCCR) 2] (R = H, trans-3; Me = trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac)2(Ph2PCCR) 2] (R = Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph2PCCPPh2 with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac)2(-Ph2PCCPPh2)]n (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac)2(-Ph2PCCPPh 2)}2] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac) 2L2] (L = PPh3, PPh2Me). Electrochemical studies of cis-6 show two reversible RuII/III oxidation processes separated by 300 mV, the estimated comproportionation constant (Kc) for the equilibrium cis-62+ + cis-6 2(cis-6+) being ca. 105. However, UV-Vis spectra of cis-6+ and cis-62+, generated electrochemically at -50 °C, indicate that cis-6+ is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF6 to trans-3 and trans-4 forms the green air-stable complexes trans-3·PF6 and trans-4·PF6, respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4·PF6 and cis-6 have been confirmed by X-ray crystallography.

AB - Two equivalents of Ph2PCCR (R = H, Me, Ph) react with thf solutions of cis-[Ru(acac)2(η2-alkene)2] (acac = acetylacetonato; alkene = C2H4, 1; C 8H14, 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac)2(Ph2PCCR) 2] (R = H, trans-3; Me = trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac)2(Ph2PCCR) 2] (R = Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph2PCCPPh2 with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac)2(-Ph2PCCPPh2)]n (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac)2(-Ph2PCCPPh 2)}2] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac) 2L2] (L = PPh3, PPh2Me). Electrochemical studies of cis-6 show two reversible RuII/III oxidation processes separated by 300 mV, the estimated comproportionation constant (Kc) for the equilibrium cis-62+ + cis-6 2(cis-6+) being ca. 105. However, UV-Vis spectra of cis-6+ and cis-62+, generated electrochemically at -50 °C, indicate that cis-6+ is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF6 to trans-3 and trans-4 forms the green air-stable complexes trans-3·PF6 and trans-4·PF6, respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4·PF6 and cis-6 have been confirmed by X-ray crystallography.

UR - https://www.scopus.com/pages/publications/34247335876

U2 - 10.1039/b618365d

DO - 10.1039/b618365d

M3 - Article

SN - 1477-9226

SP - 1677

EP - 1686

JO - Dalton Transactions

JF - Dalton Transactions

IS - 17