Moni- and di(tertiary phosphine and arsine) complexes of ruthenium(II) and ruthenium(III)

Mague, Joel T.; Mitchener, Joseph P.

doi:10.1021/ic50117a028

Cited by 40 publications

(10 citation statements)

References 7 publications

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“…These data allow us to propose that (2) is a five-co-ordinate ruthenium(0) complex containing one bidentate and one monodentate dppm group. Complexes of palladium and platinum showing some similarities, and in particular con-Scheme.…”

Section: Reaction Of [Ru(cod)(cot)] With Dppm (See Scheme)-mentioning

confidence: 83%

Bis(diphenylphosphino)methane complexes of ruthenium(0) and ruthenium(II)

Chaudret¹,

Commenges²,

Poilblanc³

1984

J. Chem. Soc., Dalton Trans.

141

105

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Section: Reaction Of [Ru(cod)(cot)] With Dppm (See Scheme)-mentioning

confidence: 83%

Bis(diphenylphosphino)methane complexes of ruthenium(0) and ruthenium(II)

Chaudret¹,

Commenges²,

Poilblanc³

1984

J. Chem. Soc., Dalton Trans.

141

105

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“…Chemical shifts are given in parts per million (ppm) relative to internal SiMe 4 ( 1 H, 13 C) or external 85% H 3 PO 4 ( 31 P). The complexes 1a , 1b − e , 1f , and [AuCl(PPh 3 )] were prepared as described elsewhere.…”

Section: Methodsmentioning

confidence: 99%

“…With the aim of accomplishing the synthesis of high nuclearity heterometallic species (lastly polymers) in a controlled manner, via methanide intermediates, we have now explored the chemistry of the bis(dppm) derivatives trans- [RuCl(L)(dppm) 2 ] + ( 1a − c , L = CO, CNR; R = t Bu and Ph), , trans- [Ru(CNR) 2 (dppm) 2 ] 2+ ( 1d , e ) 4 and trans- [Mn(CO) 2 (dppm) 2 ] + ( 1f ) . Notably, we have been able to obtain di-, tri-, tetra-, and pentametallic species by stepwise double metalation of the two coordinated dppm ligands.…”

Section: Introductionmentioning

confidence: 99%

High Nuclearity Heterometallic Gold(I)-Containing Derivatives from Manganese(I) and Ruthenium(II) dppm Complexes via Diphosphinomethanide Intermediates

et al. 1997

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The cationic complexes trans-[RuCl(L)(dppm)2]+ (1a, L = CO; 1b, L = CNtBu; 1c, L = CNPh), trans-[Ru(CNR)2(dppm)2]2+ (1d, R = tBu; 1e, R = Ph), and trans-[Mn(CO)2(dppm)2]+ (1f) are selectively deprotonated with KOH or NaMeO affording the mixed ligand dppm/dppm-H complexes (dppm-H = [(PPh2)2CH]-) trans-[RuCl(L)(dppm)(dppm-H)] (2a − c), trans-[Ru(CNR)2(dppm)(dppm-H)]+ (2d,e), and trans-[Mn(CO)2(dppm)(dppm-H)] (2f), respectively. Under more forcing conditions, 2d and 2e undergo a second deprotonation reaction to give trans-[Ru(CNR)2(dppm-H)2] (3d,e). The treatment of 1f with [AuCl(PPh3)] in the adequate stoichiometric ratio, in the presence of an excess of KOH, affords the heterometallic complexes trans-[Mn(CO)2(dppm){(PPh2)2CH(AuPPh3)}]+ (4f), trans-[Mn(CO)2{(PPh2)2CH(AuPPh3)}2]+ (5f), trans-[Mn(CO)2{(PPh2)2CH(AuPPh3)}{(PPh2)2C(AuPPh3)2}]+ (6f), and trans-[Mn(CO)2{(PPh2)2C(AuPPh3)2}2]+ (7f) as a result of the stepwise double metalation of the two dppm ligands. 4f is more conveniently prepared by reaction of 2f with an excess of [AuCl(PPh3)], although a good purification of the complex is not achieved. For 5f, two isomers are present, in the same proportion, corresponding to the mutually syn or anti disposition of the two Au(PPh3) fragments. By contrast, in the treatment of the ruthenium derivatives 1d and 1e with [AuCl(PPh3)] in the presence of KOH, the products of partial metalation of the dppm ligands were not obtained and only the fully metalated pentametallic species trans-[Ru(CNR)2{(PPh2)2C(AuPPh3)2}2]2+ (7d and 7e) were isolated. For 2a and 7e, an X-ray diffraction study was undertaken.

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“…The chemistry of Ru(II) complexes [RuX 2 (CO) n (P) 2 ] (X = H, Cl; n = 1,2) with P donors in trans position is well-known and widely explored . In particular, complexes bearing bulky phosphines such as P t Bu 2 Me or P i Pr 3 are currently receiving considerable interest because of their ability to form coordinatively unsaturated complexes with unique properties. − Surprisingly, the chemistry of the analogous cis phosphine complexes is barely explored and the number of known compounds is very small. − Therefore, we investigated the properties and reactivity of [RuX 2 (CO) n (PP)] (X = H, Cl; n = 1,2) with P donors occupying cis positions. To enforce the cis position of the P atoms and to stabilize potential coordinatively unsaturated complexes, we choose the bulky chelate ligand d t bpe ( t Bu 2 PC 2 H 4 P t Bu 2 ) …”

Section: Introductionmentioning

confidence: 99%

“…[2][3][4][5] Surprisingly, the chemistry of the analogous cis phosphine complexes is barely explored and the number of known compounds is very small. [6][7][8][9] Therefore, we investigated the properties and reactivity of [RuX 2 (CO) n (PP)] (X ) H, Cl; n ) 1,2) with P donors occupying cis positions. To enforce the cis position of the P atoms and to stabilize potential coordinatively unsaturated complexes, we choose the bulky chelate ligand d t bpe ( t Bu 2 -PC 2 H 4 P t Bu 2 ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Ru(II)/Chloro/Hydrido/Carbonyls with Cis Bulky Phosphines: An Unsaturated Ru(II) Monohydride

1999

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[RuCl2(CO)2(d t bpe)], d t bpe = tBu2PCH2CH2PtBu2 is synthesized as a mixture of two isomers and is converted to [RuHCl(CO)2(d t bpe)], then [Ru(H)2(CO)2(d t bpe)]. The chloride trans to hydride in [RuHCl(CO)2(d t bpe)] can be replaced by BF4 - or PF6 -, and reaction with NaB(3,5-(CF3)2C6H3)4 gives authentic, five-coordinate [RuH(CO)2(d t bpe)]+, characterized structurally by X-ray diffraction, which reveals the lack of agostic interactions. [Ru(H)2(CO)2(d t bpe)] reacts under mild conditions with CO to give [Ru(CO)3(d t bpe)], with ethylene to give C2H6 and [Ru(C2H4)(CO)2(d t bpe)], and with D2 to give some [Ru(H)(D)(CO)2(d t bpe)]. These results are interpreted in terms of relatively facile dissociation of one end of d t bpe from the metal.

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Moni- and di(tertiary phosphine and arsine) complexes of ruthenium(II) and ruthenium(III)

Cited by 40 publications

References 7 publications

Bis(diphenylphosphino)methane complexes of ruthenium(0) and ruthenium(II)

Bis(diphenylphosphino)methane complexes of ruthenium(0) and ruthenium(II)

High Nuclearity Heterometallic Gold(I)-Containing Derivatives from Manganese(I) and Ruthenium(II) dppm Complexes via Diphosphinomethanide Intermediates

Synthesis and Reactivity of Ru(II)/Chloro/Hydrido/Carbonyls with Cis Bulky Phosphines: An Unsaturated Ru(II) Monohydride

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