The synthesis and crystallographic characterisation of the complexes [RuX(CO)(η2-C,N-C6H5C(H) NC6H4-4Me)(PPh3)2] · CHCl3 (X = Cl, Br, I, F): Evidence for competing Ru–X⋯Cl–CHCl2 and Ru–X⋯HCCl3 interactions in the solid state

Flower, Kevin R.; Leal, Laura G.; Pritchard, Robin G.

doi:10.1016/j.jorganchem.2005.04.026

Cited by 6 publications

(2 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…3. This type of Cl 3 CHÁ Á ÁClRu interaction was observed in the related complexes [RuX(CO)(g 2 -C,ıN-C 6 H 4 CH@NC 6 H 4 -4R)-(PPh 3 ) 2 ] Á HCCl 3 (X = F, Cl, Br, I; R = NO 2 , Me) [16][17][18]. The non-conventional Cl 3 CHÁ Á ÁClRu hydrogen bonds in 1 are shorter than those observed in [RuX-(CO)(g 2 -C,N-C 6 H 4 CH@NC 6 H 4 -4R)(PPh 3 ) 2 ] Á HCCl 3 (X = F, Cl, Br, I; R = NO 2 , Me) and this presumably results from less steric congestion about the Cl atom in the absence of the aromatic ring attached to the heteroatom allowing closer approach.…”

Section: Introductionsupporting

confidence: 54%

The synthesis, reactivity and modelling studies of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]: Crystal and molecular structures of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]·3.5CHCl3 and [Ru(NCtBu)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4]·2CHCl3

Flower¹,

Garrould²,

Leal³

et al. 2008

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

Section: Introductionsupporting

confidence: 54%

The synthesis, reactivity and modelling studies of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]: Crystal and molecular structures of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]·3.5CHCl3 and [Ru(NCtBu)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4]·2CHCl3

Flower¹,

Garrould²,

Leal³

et al. 2008

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

“…Halides in this regard are particularly promising in that they can act as a ligand (and so change the sterics and electronics at the metal center), and also engage, to different extents based on the identity of the halide, in hydrogen bonding interactions. [19][20][21][22][23][24][25][26][27] Thus, halides, among the most common ligands/counter ions found in transition metal catalysis, can play an important role in controlling the position of the MLPT equilibrium.…”

Section: Introductionmentioning

confidence: 99%

The underappreciated influence of ancillary halide on metal–ligand proton tautomerism

et al. 2022

View full text Add to dashboard Cite

show abstract

Reactivity Diversification – Synthesis and Exchange Reactions of Cobalt and Iron 2‐Alkenylpyridine/‐pyrazine Complexes Obtained by Vinylic C(sp²)–H Activation

et al. 2015

View full text Add to dashboard Cite

The reactivity of 2‐alkenylpyridine derivatives with trimethylphosphane‐supported iron– and cobalt–methyl adducts were investigated and provided a series of C,N‐cyclometalated complexes through smooth vinyl C(sp2)–H activation. The reactions of Co(CH3)(PMe3)4 with 2‐vinylpyridine, 2‐(1‐phenylvinyl)pyridine, and 2‐vinylpyrazine provided dark green crystals of the five‐membered metallacycles (κ2‐C,N‐R1R2C=CH)Co(PMe3)3 (1: R1 = C5H4N, R2 = H; 2: R1 = C5H4N, R2 = Ph; 3: R1 = C4H3N2,R2 = H). The oxidative addition of 1–3 with iodomethane afforded the mer‐trans trivalent cobalt complexes (κ2‐C,N‐R1R2C=CH)Co(CH3)I(PMe3)2 (4: R1 = C5H4N, R2 = H; 5: R1 = C5H4N, R2 = Ph; 6: R1 = C4H3N2, R2 = H) in modest yields. The reaction of 2 with an additional equivalent of 2‐(1‐phenylvinyl)pyridine incorporated a second C,N metallacycle with an η2‐bonded alkenyl moiety to provide (κ2‐C,N‐C5H4N–CH=CH)(κ3,η2‐C,C,N‐C5H4N–CH=CH2)Co(PMe3) (7). No cyclometalation was observed with 8‐vinylquinoline and Co(CH3)(PMe3)4, which afforded (κ3,η2‐C,C,N‐C9H6N–CH=CH2)Co(CH3)(PMe3)2 (8) with retention of the Co–CH3 group; therefore, a suitable bite angle is required for C–H activation. No N coordination was observed with Fe(CH3)2(PMe3)4 and 8‐vinylquinoline (reductive elimination of C2H6), which afforded a low‐valent Fe(PMe3)3 moiety bound in an η4‐fashion with the exocyclic vinyl group and the ortho‐carbon atoms to give (κ4,η4‐C,C,C,C‐C9H6N–CH=CH2)Fe(PMe3)3 (9). In polar solvents, an equilibrium of cyclometalated 7,8‐benzoquinoline exists between the mer‐trans (90 %) and mer‐cis (10 %) configurations of (κ2‐C,N‐C13H6N)Fe(CH3)(PMe3)3 (10). At variance with the previously reported bicyclometalation of 2‐(2‐naphthalene‐1‐ylvinyl)pyridine with iron adducts, similar reactions with methylcobalt species provided the monocyclometalated η2,σ1‐bound coordination motif (κ3,η2‐C,C,N‐C5H4N–CH=CH–C10H6)Co(PMe3)2 (11). The reaction of 11 with carbon monoxide provided the monocarbonyl complex (κ3,η2‐C,C,C‐C5H4N–CH=CH–C10H6)Co(CO)(PMe3)2 (12), accompanied by the release of the N‐coordination site. The carbonylation of (κ3‐C,C,N‐C5H4N–CH=C–C10H6)Fe(PMe3)3 resulted in the exchange of one PMe3 ligand with the retention of the coordination sites to generate (κ3‐C,C,N‐C5H4N–CH=C–C10H6)Fe(CO)(PMe3)2 (13). All new compounds were identified by NMR spectroscopy and structurally characterized by single‐crystal X‐ray crystallography (with the exception of 10 and 13).

show abstract

The synthesis and crystallographic characterisation of the complexes [RuX(CO)(η2-C,N-C6H5C(H) NC6H4-4Me)(PPh3)2] · CHCl3 (X = Cl, Br, I, F): Evidence for competing Ru–X⋯Cl–CHCl2 and Ru–X⋯HCCl3 interactions in the solid state

Cited by 6 publications

References 24 publications

The synthesis, reactivity and modelling studies of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]: Crystal and molecular structures of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]·3.5CHCl3 and [Ru(NCtBu)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4]·2CHCl3

The synthesis, reactivity and modelling studies of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]: Crystal and molecular structures of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]·3.5CHCl3 and [Ru(NCtBu)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4]·2CHCl3

The underappreciated influence of ancillary halide on metal–ligand proton tautomerism

Reactivity Diversification – Synthesis and Exchange Reactions of Cobalt and Iron 2‐Alkenylpyridine/‐pyrazine Complexes Obtained by Vinylic C(sp²)–H Activation

Contact Info

Product

Resources

About

The synthesis and crystallographic characterisation of the complexes [RuX(CO)(η2-C,N-C6H5C(H) NC6H4-4Me)(PPh3)2] · CHCl3 (X = Cl, Br, I, F): Evidence for competing Ru–X⋯Cl–CHCl2 and Ru–X⋯HCCl3 interactions in the solid state

Cited by 6 publications

References 24 publications

The synthesis, reactivity and modelling studies of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]: Crystal and molecular structures of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]·3.5CHCl3 and [Ru(NCtBu)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4]·2CHCl3

The synthesis, reactivity and modelling studies of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]: Crystal and molecular structures of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]·3.5CHCl3 and [Ru(NCtBu)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4]·2CHCl3

The underappreciated influence of ancillary halide on metal–ligand proton tautomerism

Reactivity Diversification – Synthesis and Exchange Reactions of Cobalt and Iron 2‐Alkenylpyridine/‐pyrazine Complexes Obtained by Vinylic C(sp2)–H Activation

Contact Info

Product

Resources

About

Reactivity Diversification – Synthesis and Exchange Reactions of Cobalt and Iron 2‐Alkenylpyridine/‐pyrazine Complexes Obtained by Vinylic C(sp²)–H Activation