Electrochemical Studies on [Mn(CNR),]+ Complexes derivative with Mn CO 5X X = Br or Cl) gave only with C5H5Mo(N0)2Cl in diethyl ether gave an unidentified yellow solid suggested by its NMR spectrum to contain (CH3),Sn groups but neither C5H5 nor (CH3)2C groups. Reaction of (CH3)2C=NOSn(CH3)3 with C5H5Fe(CO)2C1 in boiling benzene gave only (CH3)3SnFe(C0)2C5H5.'' No tractable products were obtained from reactions of (CH3)2-in ethereal solvents at or near room temperature. These observations suggest that the range of transition metal systems to which (CH3)2C=NOSn(CH3)3 can transfer (CH3)2CN0 groups is extremely limited and that in some cases this tin reagent instead transfers (CH3)$n or possibly (CH3),Sn0 units to the transition metal system. Acknowledgment. We are indebted to the National Science Foundation for partial support of this work under Grant CHE-75-19974. We are also indebted to M and T Chemical Co. for generous gifts of trimethyltin chloride. Registry No. MezCNOMo(CO)zCp, 61491-36-9; (CH2)&!NOMo(C0)2Cp, 61 81 3-21-6; (CHz=CH)(Me)CNOMo-(CO)zCp, 618 13-22-7; (MezC=CH)(Me)CNOMo(CO)zCp, 61813-23-8;CHz=CH(CH2)zC(Me)NOMo(CO)2Cp, 61813-24-9; (CH3)3SnMn(CO)5.' 0 ' Reaction of (CH3)2C=NOSn(CH3)3 Me2CNOW(C0)zCp, 6 18 13-25-0; (CH2)5CNOW(C0)2Cp, 618 13-26-1; (CHz=CH)(Me)CN0W(CO),Cp, 618 13-27-2; (MezC=CH)(Me)CNOW(CO)2Cp, 61 81 3-28-3; CH2=CH-(CHz)zC(Me)NOW(CO)zCp, 61813-29-4; (CH3)zC==NOSn(CH3)3, 25092-7 1-1; (CH3)zC=CHC(CH3)=NOSn(CH3)3, 61 8 12-49-5; HzC=CH(CH2)zC(CH3)=NOSn(CH3)3, 61812-50-8; CSHS-
Abstract. The reactions of Mn(CO)._.(CNMe).Br (n = 2, 3, 4) with either CO or CNMe in the presence of a halide acceptor are found to be stereospecific, with incoming ligand replacing the halide ion. These reactions were used in the syntheses of mer-and fac-[Mn(CO),(CNMe),]PF. and cis-and trans-[Mn(CO).(CNMe).)PF•. A cyclicvoltammetric study showed that the isomeric complexes had different E ' 12 values. The difference in eases of oxidation was rationalized qualitatively based on the abilities of CO and CNMe to serve as 1F acceptors. This suggestion was supported quantitatively by theoretical calculations which defined the degree of stabilization of the HOMO levels in these complexes through 1F bonding.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.