Synthesis of Ruthenium Phenylindenylidene, Carbyne, Allenylidene and Vinylmethylidene Complexes from (PPh3)(3-4)RuCl2: A Mechanistic and Structural Investigation

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Chemistry and Biochemistry


The reaction of (Ph3P)(3)RUCl2 with 1,1-diphenyl-2-propyn-l-of was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh3)(2)Cl2Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C-3-spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh3)(2)ClRu(mu-Cl)(3)(PPh3)(2)Ru=C=C=CPh2 complex (5). The reaction of (Ph3P)(3-4)RUCl2 with 1,1-diphenyl-2-propyn-l-of in CH2Cl2 or C2H4Cl2 under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh3)(2)Cl3Ru C-CH=CPh2 carbyne complex (7), an HCl adduct of previously elusive (PPh3)(2)Cl2Ru=C=C=CPh2 complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C3-spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H2O) to give hexacoordinate (PPh3)(2)Cl-2(ROH)Ru=C=C=CPh2 (R = H, CH3, C2H5) complexes (9)-(11) with the O-donor coordinating in trans-position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-(N,N-dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh3)(2)Cl-2(DMAP)Ru=C=C=CPh2 complex (12) with one molecule DMAP also coordinating in trans-position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh3)(2)Cl2Ru=C(OCH3)-CH=CPh2 (14) and (PPh3)(2)Cl2Ru=C(OAc)-CH=CPh2 (15) where the nucleophile added to the alpha-carbon atom. The structures of complexes 5, 7, 9-11, 14, and 15 were solved via X-ray crystallography. Published by Elsevier B.V.

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Journal of Organometallic Chemistry





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