- 作者: Adams, Richard D. ; 陳林楓 ; 黃明生
- 作者服務機構: Dept. of Chemistry and Biochemistry, Univ. of South Carolina, Columbia, South Carolina, U.S.A.
- 中文摘要: The reaction of (OC)/sub 4/Re [ .mu.-E-HC=C(CO/sub 2/ Me)CS/sub 2/ ] Re(CO)/sub 4/ (1) with EtNH/sub 2/ yielded two new complexes: Re(CO)/sub 4/ [ C(H)=C(CO/sub 2/Me) C(NHEt)=S ] (2), (52%) and Re(CO)/sub 3/(NH/sub 2/Et) [ C(H)=C(CO/sub 2/Me)C(NHEt)= S ] (3a) (24%) by competitive attack of the EtNH/sub 2/ at the dithiocarboxylate grouping and at the hydrogen substituted olefinic carbon atom in (1). In both cases there is a loss of one of the rhenium groupings. The reaction of the sulfurized and oxygenated derivatives of (1), (OC)/sub 4/Re [ EC(H)C(CO/sub 2/Me)CS/sub 2/ ] Re(CO)/sub 4/ (4a) (E=S), (4b) (E=O) with EtNH/sub 2/ yielded Re(CO)/sub 4/ [ C(H)=C(CO/sub 2/Me)C(NHEt)=S ] (5a), the parent carbonyl of (3a), by exclusive attack of the amine at the hydrogen substituted olefinic carbon atom. The reaction of (OC)/sub 4/Re [ .mu.-SC(S)C(CO/sub 2/Me)C(H)S ] Re(CO)/sub 4/ (6a) (an isomer of 4a) with EtNH/sub 2/ produced a similar result. The reaction of (4a) with Et/sub 2/NH yielded Re( CO)/sub 4/ [ .mu.-S/sub 2/C=C(CO)/sub 2/Me)C=NEt/sub 2/ ] (5b) an N-ethyl substituted derivative of (5a). These results indicate that the addition of certain heteroatoms can have a directing effect upon the reactivity of these compounds with amines. Compounds (2) and (5a) were characterized by single crystal X-ray diffraction analyses. Crystal Data: For (2): space group =P.1bar., a=10.782(1).ANG., b=14.721(2).ANG., c=9.940(2).ANG., .alpha.=91.57(1).degree., .beta.=93.61(1).degree., .gamma.=70. 774(9).degree., Z=4, 4516 reflections, R=0.047 and for (5a): space group =P2/sub 1//n, a=11.389(2).ANG., b=9.660(2).ANG., c=14.756(3).ANG., .beta.=103.36(2).degree., Z=4, 1601 reflections, R=0.022.
- 英文摘要: --
- 中文關鍵字: Dimetalated Olefin; Rhenium; Dithiocarboxylate; Amine; Thioamido Complex; Single Crystal X-Ray Diffraction
- 英文關鍵字: 雙金屬烯;錸;二硫羧酸;胺;硫胺基錯合物;單晶X射線繞射