Synthesis of New Ruthenium(II) Carbonyl Hydrido, Alkenyl, and Alkynyl Complexes with Chelating Diphosphines

Synthesis and Reactivity of Ru(NHC)(dppp)(CO)H2 and Ru(NHC)(dppp)(CO)HF Complexes: C–H and C–F Activation

“…[10,11] The IR carbonyl-stretching frequency of 1900 cm -1 is lower than that reported for [Ru(PPh 3 )-(dppp)(CO)HCl] (1920 cm -1 ) consistent with fluoride being a stronger π-donor. [12] The molecular structure of 1 was determined by X-ray crystallography as shown in Figure 1. Selected bond lengths and angles are given in Table 1.…”

“…The compound displayed a distorted-octahedral geometry with the two, trans-phosphanes being tilted towards the hydrido ligand [P(1)-Ru(1)-P(3) 168.09(3)°; P(4)-Ru(2)-P(5) 171.20(3)°]. [12,13] The Ru-F bond lengths for the two molecules in the unit cell [2.1005(18), 2.0943(18) Å] are comparable to other hydrido fluorido Ru complexes in the literature [14,15] and in fact identical to the Ru-F distance in [Ru(PPh 3 ) 3 (CO)HF] [9] (unsurprisingly given that in both cases the π-donor fluorido ligand is trans to the π-acceptor CO group).…”

“…This species was reported by us some time ago upon thermolysis of the dihydrido complex [Ru(IMes)(dppp)(CO)H 2 ] (4) in the presence of an alkene. [5] As the mixture of 2 and 3 proved to be inseparable, an Ru(2)-C(47) 1.820(4) Ru(2)-P(6) 2.4396(9) Ru(2)-F(2) 2.0943(18) Ru(2)-P(5) 2.3418(9) Ru(2)-P(4) 2.3752(9) P(4)-Ru(2)-P(6) 97.39(3) P(5)-Ru(2)-P(6) 91.40(3) P(4)-Ru(2)-P(5) 171.20(3) C(47)-Ru(2)-F(2) 173.39 (12) alternative synthetic route to 2 involving reaction of 4 with Et 3 N·HF was employed. The complex displayed a single hydride resonance at ca.…”

Comparative reactivity studies of dppf-containing CpRuII and (C6Me6)RuII complexes towards different donor ligands (dppf=1,1′-bis(diphenylphosphino)ferrocene)

“…d 6 Ru II complexes containing dppf are known [7] with about 20 crystallographic reports. These include threelegged piano-stool structures [(C 5 R 5 )Ru(dppf)H] (R ¼ Me [8]; R ¼ H [9]), [(g 6 -arene)Ru(dppf)Cl]PF 6 (arene ¼ HMB [10], p-cymene [11]), [(g 6 -Me 4 -C 6 H 2 )RuCl 2 ] 2 (ldppf) Á CH 2 Cl 2 [10], [CpRu(dppf)(CBC-(C 5 H 4 NH))-W(CO) 4 (PPh 3 )] [12], [TpRu(dppf)Cl] and [Tp(dppf) Ru@C@C@CPh 2 ]SbF 6 [13] (Tp ¼ tris(pyrazolyl)borate), a four-legged piano-stool complex [Cp*Ru(dppf)(g 2 -O 2 )]BF 4 [14], and other octahedral structures [Ru-(dppf)(bipy) 2 ](PF 6 ) 2 [15], [Ru(dppf)(CO)(PPh 3 )(Cl)H] [16], [Ru(dppf)(CO)(NCMe)(PPh 3 )H]BF 4 Á EtOH [17], [Ru(dppf)(C 3 H 5 )(C 6 F 5 O 2 )] [18], [RuCl(CO)(dppf) (PPh 3 )]BF 4 and [RuCl(CO)(dppf)(CH 3 CN)] 2 (BF 4 ) 2 [19]. In this paper we report complexes obtained by chloro substitution in [CpRu(dppf)Cl] (1) and [(HMB)Ru(dppf)Cl](PF 6 ) (3), and structural variations in response to the aromatic ring ligand.…”

Ruthenium-catalyzed cycloisomerization of 1,1,2,2-tetramethyl-1,2-divinyldisilane: Selective formation of a five-membered silacycle

“…1,1,2,2-Tetramethyl-1,2-divinyldisilane (1) [11], ruthenium catalysts 4 [12], 5 [13], 6 [14], 7-11 [15], 12 [9], and Et 3 SiD [16] were prepared as reported in the literature. Other reagents were commercially available and used without further purification.…”