Structure of organoruthenium-derived Langmuir monolayers at the air–water interface: a molecular-modelling approach

Syntheses and molecular structures of group 8 benzonitrile complexes

“…The complex salts [Ru(NCPh)(PPh 3 ) 2 Cp]PF 6 (1), [Ru(NCPh)(dppe)Cp*]PF 6 (2) and [Fe(NCPh)(dppe) Cp]PF 6 (3) (Chart 1) were synthesised in good yield from the reaction of the corresponding chloride complexes with 0022-328X/$ -see front matter Ó 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jorganchem.2005.08.002 a 3-fold excess of benzonitrile in methanol solutions containing NH 4 PF 6 , and crystallised by slow diffusion of methanol (1,3) or hexane (2) into concentrated CH 2 Cl 2 solutions. The substituted derivatives [Ru(NCC 6 H 4 NO 2 -4)-(PPh 3 ) 2 Cp]PF 6 (4) and [Ru(NCC 6 H 4 NMe 2 -4)(PPh 3 ) 2 Cp]-PF 6 (5) were readily prepared in an entirely analogous procedure from the stoichiometric reaction of RuCl(PPh 3 ) 2 Cp with 4-nitrobenzonitrile or 4-(dimethylamino)benzonitrile, respectively.…”

“…A wide variety of nitriles have been shown to displace the halide ligand (X) from iron and ruthenium complexes MX(L 2 )Cp to afford cations [M(NCR)(L 2 )Cp] + , which are readily isolated as the corresponding BF À 4 or PF À 6 salts from reactions carried out in methanol or acetone [1][2][3][4]6,7,17,[20][21][22]. The complex salts [Ru(NCPh)(PPh 3 ) 2 Cp]PF 6 (1), [Ru(NCPh)(dppe)Cp*]PF 6 (2) and [Fe(NCPh)(dppe) Cp]PF 6 (3) (Chart 1) were synthesised in good yield from the reaction of the corresponding chloride complexes with 0022-328X/$ -see front matter Ó 2005 Elsevier B.V. All rights reserved.…”

“…The interest in nitrile ligand chemistry has undergone something of a renaissance in recent years, spurred on by observations of significant second order non-linear optical responses [1][2][3][4][5][6][7][8], the desire to rationalise and exploit the greatly enhanced electrophilicity of the nitrile carbon centre when coordinated to an electron-rich metal centre [9][10][11], and the rigid-rod like structure of the M-N-C moiety [12]. Nitriles are isoelectronic with acetylide anions and, unsurprisingly, similar interests have prompted many investigations of the synthesis, molecular structure, reactivity, optical and magnetic properties and electronic structure of metal acetylide complexes [13][14][15][16][17].…”

Phosphine substitution reactions of (η5-cyclopentadienyl)ruthenium bis(triarylphosphine) chloride, CpRu(PAr3)2Cl {PAr3= PPh3, P(p-CH3C6H4)3, P(p-FC6H4)3, P(p-CH3OC6H4)3, and PPh2(p-CH3C6H4)}: a tale of two mechanisms

“…Benzene-d 6 (Cambridge Isotope Laboratories) and chloroform-d (Acros) were purified by refluxing over Na/benzophenone and P 2 O 5 , respectively, and distilled prior to use. Ruthenium(II) compounds CpRu(PPh 3 ) 2 Cl (1a), 8 CpRu(PPh 2 -{p-CH 3 C 6 H 4 }) 2 Cl (1b), 9 CpRu(P{p-CH 3 C 6 H 4 } 3 ) 2 Cl (1c), 10 CpRu(P{p-CH 3 OC 6 H 4 } 3 ) 2 Cl (1d), 11 CpRu(P{p-FC 6 H 4 } 3 ) 2 Cl (1e), 12 and CpRu(PPh 3 )(PMePh 2 ) Cl (2a), 13 were prepared by literature procedures. Melting points were determined in capillary tubes on an Electrothermal 9110 melting point apparatus and are uncorrected.…”