Some new π-cyclopentadienylruthenium complexes

Abstract

Synthesis of the complexes (n-C6H5)Ru(L),CI [L = PPh,, PPh,Me, P(OMe),, AsPh,] and the related osmium compound (n-C6H5)0s(PPh3),Br are described. Reactions of (w-C5H6)Ru( PPh3),CI of three types were investigated: (a) replacement of the CI atom by, e.g. H, Me, C6Fs, or SnCI, groups; ( b ) replacement of one of the phosphine ligands by,e.g. CO, PPh,Me; (c) formation of cationiccomplexes of the type [(w-CsH6) Ru(PPh,),L] +, e.g. L = CO, MeCN. Twounusual complexes, (n-C5H6)Ru(PPh,)2BH,, and the hexachlorodizincate, [(r-C,H,) -Ru(PPh,),(MeCN)],Zn,CI,.are also reported.STUDIES l y 2 on ruthenium complexes containing both x-cyclopentadienyl and carbonyl ligands have shown that there is surprisingly little difference in reactivity between these complexes and the analogous ironcontaining compounds. However, the increased reactivity towards small molecules of phosphine complexes compared with carbonyl, together with the usefulness of some ruthenium@) complexes in many catalytic reaction^,^ suggested that a study of the chemistry of complexes of the type (x-C,H,)Ru(PR,),X would be worthwhile.Although (x-C,H,)Ru(CO),Cl can be readily obtained it is unlikely to be a useful precursor for compounds of the type (x-C5H5)Ru(PR3),X in view of work with the iron compounds (x-C,H,)Fe( CO),X which has shown that monodentate phosphines react to give only monocarbonyl complexes (x-C,H,)Fe(CO) (PR3)X.4* Only with triphenyl phosphite under forcing conditions have any fully substituted complexes of the type (x-C,H,)-Fe[P(OPh),],X been obtained.' Moreover, it has re-

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

“…The closest available structure for comparison is that of [CpRu(PPh 3 ) 2 (NCS)] [31] which also features an N-bound NCS ligand. The Ru-N bond distances are indistinguishable in the two structures but the Ru-P bond distances in 2 (2.2978(8) and 2.2922 (7) A) are significantly shorter than those in [CpRu(PPh 3 ) 2 (NCS)] (2.318(1) and 2.323 (2) A) [31]. The distance between the ring centroid of the Ru-bound Cp ring and the metal is 1.8596 (14) A.…”

“…The 31 P resonance of dppf of the CpRu(II) complexes are observed at d 46.1-49.8, with those of complexes 8 and 9 appearing as doublets due to P-P coupling (J ¼ 42 Hz) with the monophosphine co-ligand, viz. PMe 3 and PMe 2 Ph, respectively. Correspondingly, the PMe 3 and PMe 2 Ph signals are seen as triplets due to coupling to the two P atoms of dppf.…”

“…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. (1) [CpRu(dppf)Cl] (1) was obtained as bright yellow solids in 78% yield from the reaction of [CpRu-(PPh 3 ) 2 Cl] with dppf in refluxing toluene, according to the method of Bruce et al [9]. (4) in 88% yield (shown in Scheme 1).…”

“…The organometallic chemistry of [CpRu(PR 3 ) 2 Cl] [1,2] has been extensively studied and the related g 6 -arene complexes are also known [3]. However, little is reported of their comparative reactivities.…”

Cyclopentadienyl RuII Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

“…However, the use of untreated solvent resulted in a negligible lowering of the reaction rate. The complexes [RuCl(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (1), [23] [RuH(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (2), [24] [RuI(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (3), [25] [RuN 3 (η 5 -C 5 H 5 )(PPh 3 ) 2 ] (4), [25] [Ru(SnCl 3 )(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (5), [26] [Ru(η 5 -C 5 H 5 )(CH 3 CN)(PPh 3 ) 2 ]PF 6 (6), [26] [Ru(η 5 -C 5 H 5 )(CH 3 CN) 2 (PPh 3 )]PF 6 (7), [27] [Ru(η 5 -C 5 H 5 )(CH 3 CN) 3 ]PF 6 (8), [28] [RuCl(η 5 -C 5 H 5 )(PMePh 2 ) 2 ] (9), [29] [RuCl(η 5 -C 5 H 5 ){P(mTolyl) 3 } 2 ] (10), [15] [RuCl(η 5 -C 5 H 5 )(dppe)] (11), [30] [RuCl(η 5 -C 5 H 5 )(PHPh 2 )(PPh 3 )] (12), [31] [RuCl(η 5 -C 5 H 5 )(CO)(PPh 3 )] (13), [32] [Ru(…”