(η⁶-Arene)−Ruthenium(II) Complexes Containing Methanide and Methandiide Anions of Ph₂P(═S)CH₂P(═NR)Ph₂: Unprecedented Insertion of Isocyanide into a Ruthenium−Carbene Bond

Abstract

The novel (iminophosphoranyl)(thiophosphoranyl)methane ligands Ph 2 P(dS)CH 2 P(dNR)Ph 2 (R ) 2,4,6-C 6 H 2 Me 3 (2a), 4-C 6 F 4 CHO (2b), 4-C 6 F 4 CN (2c), 4-C 5 F 4 N (2d), P(dO)(OEt) 2 (2e), P(dO)(OPh) 2 (2f), P(dS)(OEt) 2 (2g), P(dS)(OPh) 2 (2h)) have been synthesized by oxidation of the phosphine unit in Ph 2 PCH 2 P(dNR)Ph 2 with elemental sulfur. Treatment of 2a-f with Li n Bu generates the corresponding methanide anions which react in situ with [{RuCl(µ-Cl)(η 6 -p-cymene)} 2 ] to afford the mononuclear derivatives 3f)), via tridentate κ 3 (C,N,S) coordination of the anions to ruthenium. In contrast, complexes [Ru(κ 3 (C,S,S)-Ph 2 P(dS)CHP{dNP(dS)(OR) 2 }Ph 2 )(η 6 -p-cymene)][Cl] (R ) Et (4g), Ph (4h)) are selectively formed in the reactions of [{RuCl(µ-Cl)(η 6 -p-cymene)} 2 ] with the methanide anions derived from 2g-h. Deprotonation of 3a with NaH generates the carbenic derivative [Ru{κ 2 (C,N)-Ph 2 P(dS)CP(dN-2,4,6-C 6 H 2 Me 3 )Ph 2 }(η 6 -p-cymene)] ( 5), which readily reacts with an excess of 2,6-dimethylphenyl isocyanide to afford the octahedral complex [Ru{κ 2 (C,N)-Ph 2 P(S)C(CdN-2,6-C 6 H 3 Me 2 )P(N-2,4,6-C 6 H 2 Me 3 )Ph 2 }(CN-2,6-C 6 H 3 Me 2 ) 4 ] (7), via release of the arene ring and insertion of one isocyanide molecule into the RudC bond of 5. The intermediate ketenimine complex [Ru{κ 3 (C,C,N)-Ph 2 P(dS)C(CdN-2,6-C 6 H 3 Me 2 )P(dN-2,4,6-C 6 H 2 Me 3 )Ph 2 }(η 6 -p-cymene)] ( 6) could be isolated working under stoichiometric conditions. The structure of compounds 2f, 2h, 3f, 4g, and 7 has been determined by X-ray crystallography.

Geminal Dianions Stabilized by Main Group Elements

“…When reacted with stoichiometric amount of isocyanide CNR, complexes X resulting from the [2+1] addition on the Ru=C bond are formed. 124 , 125 , 126 Upon addition of excess of isocyanide, full insertion in the Ru=C bond was observed to form the ketenimine derivative, which remains bound to the Ru center. and iso-propanol did not result in the alcoholato complex, but rather in the formation of the Ru-H species.…”

Arene ruthenium(II) p-chloroacetophenone phenylthiosemicarbazone complex mediated transfer hydrogenation of ketones

“…The coordination sphere around ruthenium consists of the η 6 -p-cymene ring, sulphur, nitrogen of thiosemicarbazone and a chloride and all are disposed in a classical pseudooctahedral three-legged piano-stool geometry, similar to that of other ruthenium(II)-p-cymene complexes (Fig. 1) [23]. The phenylthiosemicarbazone ligands bind the metal center at S and N forming the five membered chelate ring with bite angle around Ru(II) ion being 81.13(9) for S(1)-Ru(1)-N(1) and bond lengths for Ru(1)-S (1) and Ru(1)-N(1) are 2.3376(12) Å and 2.130(3) Å respectively.…”

(Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis

“…49 Recently, we have focused on the analogous (iminophosphoranyl)(thiophosphoranyl)methanide ligand {CH(PPh 2 vNR)-(Ph 2 PS)} − which is isoelectronic to the bis( phosphinimino)methanide ligand but has a hard and a soft donor atom. 56 We were inspired by the work of So and coworkers, who recently reported {CH 2 (PPh 2 vNSiMe 3 )(PPh 2 vS)}, which was prepared by the reaction of the {Ph 2 PCH 2 (PPh 2 vNSiMe 3 )} with sulfur in refluxing toluene. 53 54 The aromatic derivatives of phosphine( phosphinimino) methane CH 2 (PPh 2 vNAr)(Ph 2 PS) (Ar = p-tolyl, p-tolyl) and some platinum compounds were reported in the 1990s by Elsevier.…”