Inorganic Chemistry p. 2977 - 2983 (1981)
Update date:2022-08-05
Topics:
Pickering, Ruth A.
Angelici, Robert J.
The reaction of W(CO)5CS with -SR (R = CH3, C2H5, i-C3H7, n-C4H9, or t-C4H9) followed by alkylation of the resulting dithioester anion, W(CO)5[C(=S)SR]-, by R′I (R′ = CH3 or C2H5) produces [bis(alkylthio)carbene] tungsten complexes, W(CO)5[C(SR)(SR′)], in good yield. The substituted tetracarbonyl[bis(methylthio)carbene]tungsten complexes cis-W-(CO)4[P(OCH3)3][C(SCH3) 2] and cis-W(CO)4[P(OPh)3][C(SCH3)2] are prepared by an analogous route using cis-W-(CO)4L(CS), where L = P(OCH3)3 or P(OPh)3. (Cyclic dithiocarbene)tungsten complexes may be prepared in a similar manner from W(CO)5CS, NaS(CH2)nSH (n = 2, 3, 4), and CH3I to give W(CO)5CS(CH2)nS. The carbene complex W(CO)5{C(SCH3)[SFe(CO)2Cp]} (Cp = η5C5H5) is prepared by the reaction of W(CO)5[C(=S)(SCH3)]- with CpFe-(CO)2(THF)+. Isocyanide complexes, W(CO)5CN-R, are formed when W(CO)5[C(SCH3)2] reacts with primary amines, RNH2, where R = CH3, (CH2)2CH3, CH2Ph, C6H11, and (CH2)2N(CH3)2, or the diamine NH2(CH2)3NH2. When cis-W(CO)4[P(OPh)3][C(SCH3)2] is reacted with NH2CH2Ph and NH2(CH2)3NH2, isocyanide complexes are also formed. The reaction of W(CO)5[C(SCH3)2] with secondary amines NH(CH3)2, HN(CH2)2OCH2CH2, or HN(CH2)4CH2 yields (aminothiocarbene)tungsten complexes, W(CO)5[C(SCH3)NR2]. The compound [N(C2H5)4+][W(CO)5CN -] was formed from the reaction of W(CO)5[C(SCH3)2] with [N(C2H5)4+][N3 -].
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Doi:10.1021/ol048418f
(2004)Doi:10.1016/j.tet.2004.07.032
(2004)Doi:10.1016/S0022-328X(00)86718-2
(1981)Doi:10.1021/jo00331a009
(1981)Doi:10.1021/jo00335a040
(1981)Doi:10.1002/hlca.19820650405
(1982)
