Inorganica Chimica Acta p. 1 - 11 (1998)
Update date:2022-08-04
Topics:
Hartl, Frantiek
The five-coordinate anion [Mn(CO)3(DBCat)]- has been found to undergo nucleophilic CO substitution reactions with L = PR3, P(OR)3 producing the dicarbonyl derivatives [Mn(CO)2(L)(DBCat)]-. The reaction yield is higher for better nucleophiles such as L = PEt3 and P(OEt)3; the latter species reacts quantitatively even when added in an equivalent amount. Contrary to this, bulky phosphines with the cone angle θ≥ 145°, namely L = PPh3, PCy3, do not show this reaction but interact reversibly with [Mn(CO)3(DBCat)]- at low temperatures to give the six-coordinate adducts [Mn(CO)3(DBCat) · L]-. For L = pyridine the corresponding adduct is already formed at room temperature. Similarly, [Mn(CO)2(P(OEt)3)(DBCat)]- takes up reversibly P(OEt)3. The spectroscopic and redox properties of the adducts closely correspond with those of the invariably six-coordinate anions [Re(CO)4-n(L)n(DBCat)]- (n = 1, 2). The uptake of a Lewis base by [Mn(CO)3(DBCat)]- is facilitated by an electrophilic attack at the oxygen lone pairs of the σ,π-donor DBCat ligand. Examples are the anions [Mn(CO)3(L)(DBCat·BF3)]- (L = THF, PPh3) and [Mn(CO)3(PPh3) (DBCat·CS2)]- which are inherently stable at ambient temperature. This reactivity is closely related to the DBCat-localized le oxidation of [Mn(CO)3(DBCat)]- producing six-coordinate radical s [Mn(CO)3(L)(DBSQ)]. The electrophilic attack of CS2 at the DBCat ligand has also been documented by the conversion of [Mn(CO)3(DBCat)]- in the absence of PPh3 to the trithiocarbonate complex [Mn(CO)4(S2CS)]- and uncoordinated 4,6-di-tert-butyl-1,3-benzdioxol-2-thione. 1998 Elsevier Science S.A.
View MoreContact:0512-63006287
Address:no.88.YISHENG Road,etdz-WUJIANG,SUZHOU,CHINA
Jinan Jiaquan Chemical Co.,Ltd
Contact:+86-531-62318366
Address:Room 502 of Yidonghuayuan No.601 Huaxin Road Licheng District Jinan China
Yingkou Sanzheng Organic Chemical Co. Ltd.
Contact:+86-417-3638818
Address:25 Gengxinli Village, Daqing Road, Yingkou, Liaoning, China
Contact:+86-021-50792271
Address:Building 24A, 300 Chuantu Road, Chuansha, Pudong new area, Shanghai, China, 201202
Wuhan Benjamin Pharmaceutical Chemical Co.,Ltd
Contact:86-27-52341789
Address:Room 1518 B suite, optical valley time square, No 111 Guanshan Road, Hongshan District,Wuhan,Hubei Province,China.
Doi:10.1016/j.tetlet.2012.09.045
(2012)Doi:10.1016/0031-9422(90)85068-Q
(1990)Doi:10.1016/j.ejmech.2011.01.025
(2011)Doi:10.1016/j.bmc.2011.01.042
(2011)Doi:10.1007/BF03246226
(2011)Doi:10.1021/ja00176a059
(1990)