. Can. J. Chem. 58, 1125Chem. 58, (1980. Ruthenium(I1) phthalocyanine complexes of the type RuPcL, (PC = the phthalocyaninato dianion. L = various pyridines, imidazole, dimethylformamide, dimethylsulfoxide, and acetonitrile) may be prepared generally in solution by photolysis of RuPc(C0)L' complexes in the presence of excess L (L' may be the same as L or may be a different ligand), and in some cases a s solids by extraction of crude RuPc with L. The solid RuPc(C0)L monocarbonyls can be formed from reaction of the RuPcL, complexes with carbon monoxide, as well as via an extraction procedure using L with crude RuPc(C0) formed from Ru,(CO),, and phthalocyanine.Chemical or electrochemical oxidation of the RuPcL' or monocarbonyl complexes generates a cationic ruthenium(I1) phthalocyanine radical species and not ruthenium(III), as evidenced by esr and visible spectroscopy. DAVID DOLPHIN, BRIAN R. JAMES, ALAN J. MURRAY et JOHN R. THORNBACK. Can. J. Chem. 58, 1125Chem. 58, (1980. Les complexes phthalocyanine de ruthenium(I1) du type RuPcLz (PC = dianions phthalocyaninato, L = differentes pyridines, imidazole, dimethylformamide, dimethylsulfoxyde et acetonitrile) peuvent generalement i t r e prepares en solution par photolyse des complexes de RuPc(CO)L1 en presence d'un exces de L (L' peut i t r e identique a L ou peut Ctre un ligand different) et dans certains cas ils peuvent i t r e prepares sous forme solide par extraction du RuPc brut avec L . Le solide monocarbonyle RuPc(C0)L peut i t r e forme par la reaction des complexes RuPcL, avec le monoxyde de carbone aussi bien que par le procede d'extraction utilisant L avec le RuPc(C0) brut forme partir de Ru,(CO),, et la phthalocyanine.L'oxydation chimique ou electrochimique de RuPcL, ou des complexes monocarbonyles genere un radical cationique de phthalocyanine de ruthCnium(I1) et non de ruthenium(II1) tel que mis en evidence par la rpe et la spectroscopie visible.[Traduit par le journal]

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Treatment of [Mo(q5-C5H,)(q3-C3H5)I(NO)] or [Mo(q5-C5H6)(q3-C3H5)(NO)(NCMe)][PF,] with NaS,CNR, or AgOCOC,F5 affords [Mo(qS-C5H5)(q1-C3H6)(NO)(S2CNR2)], (1 ; R = M e or Et) and [Mo(q6-C5H6)-(q3-C3H5)(NO){OC(:O)C,F,)], respectively. The structures of these compounds are discussed. Treatment of (1 ) with electrophiles (EX) gives either cyclisation products, [Mo(q6-C5H5)(CHCH,EXCH2) (NO)(S,CNR,)], [EX = C2(CN)4 or (CF,),CO] or insertion products [Mo(q6-C5H5)(EXCH2CH:CH2)(NO)(S,CNMe,)] (EX = CF3C,CF3 or SO,). Treatment of (1 ; R = Me) with HCI and SOCI, affords [Mo(q6-C5H5)CI(NO)(S,CNMe,)] and [Mo-(q5-C5H5) (C3H5SOCI,)( NO) (S,CNMe,)], respectively. The properties of (1 ) are compared with those of [Mo(q5-C5H6)(~1-C5H5)(NO)(S2CNMe,)l and [Mo(C5Hd21(NO)1.