Aryl-Oxazoline Chelates of First-Row Transition Metals Structures of {kappa-C,N-(o-C6H4)CMe2(COCH2CMe2N)}FeCl(py) and [(kappa-C,N-(o-C6H4)CMe2(COCH2CMe2N)}Cr(mu-Cl)](2)

作者：Volpe Emily C; Manke David R; Bartholomew Erika R; Wolczanski Peter T^*; Lobkovsky Emil B

来源：Organometallics, 2010, 29(24): 6642-6652.

DOI：10.1021/om100420z

Aryl-oxazoline synthons have been explored for the preparation of strong field first row transition metal chelate species With 4 4 dimethyl 2 phenyloxazoline (HPhOx) no CH bond activations afforded complexation and aside from Zn(kappa C N 4 4 Me-2 2 (o C6H4)oxazoline)(2) (Zn(PhOx)(2)) aryl coupling reactions were noted with 4 4 dimethyl 2 (2 lithiophenyl)oxazoline (LiPhOx) and MX2 [kappa N N {4 4 Me-2 (2 o C6H4) 2 oxazoline}(2)]CoCl2 (1 Co) was structurally characterized Metalations with 4 4 dimethyl 2 benzyloxazoline (PhCH(2)Ox) were prone to deprotonation as exemplified by (Me2N)(3)Ti(eta N (4 4 dimethyl (2 CHPh)oxazoline)) (2) and bis N N' (4 4 dimethyl (2 pyridylmethyl)oxazoline)Fe (3) Oxidative addition of 4 4-dimethyl 2 (2 bromophenylpropan 2 yl) oxazoline (BrPhCMe(2)Ox) to Ni(COD)(2) provided [{kappa C N (o C6H4)CMe2(COCH2CMe2N)}Ni](2) (mu Br)(2) (4(2)) With 4 4 dimethyl 2 (2 lithiophenylpropan 2 yl)oxazoline (LiPhCMe(2)Ox) salt (FeBr2) metathesis proved uncompetitive with oxazoline ring opening as exhibited by [{kappa N O C6H4CMe2C=NCMe2CH2(mu O)}BrFe{kappa N O C6H4CMe2C=NCMe2CH2(mu O)}FeBr]Li {kappa N O C6H4CMe2C=NCMe2CH2(mu O)}(DME) (5 Fe2Li) Metatheses utilizing (PhCMe(2)Ox)(2)Zn prepared from LiPhCMe(2)Ox and ZnCl2 gave structurally characterized dichromium i e [(kappa C N (o C6H4)CMe2 (COCH2CMe2N))Cr](2)(mu Cl)(2)(6(2)) and iron i e (kappa C N {(o C6H4)CMe2(COCH2CMe2N)}Fe(py)Cl (7) products Bis aryloxazoline metal complexes proved difficult to prepare with {kappa C N (o C6H4) CMe2(COCH2CMe2N)}(2)M (M = Ni 9) the only clear example although NMR evidence exists for M =Fe (8)

• 出版日期2010-12-27