Stereoselective Synthesis of 1,5,9-Triphosphacyclododecane and Tertiary Derivatives
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- 作者：Peter G. Edwards ; James S. Fleming ; and Sudantha S. Liyanage
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：July 31, 1996
- 年：1996
- 卷：35
- 期：16
- 页码：4563 - 4568
- 全文大小：197K
- 年卷期：v.35,no.16(July 31, 1996)
- ISSN：1520-510X
文摘
Selective oxidation of Mo(CO)3 complexes oftritertiary 1,5,9-triphosphacyclododecane macrocycles (R3L)byhalogens (X2 = Cl2, Br2,I2) to Mo(II) triphospha macrocycle complexes of thetype (R3L)Mo(CO)2X2 [R=(CH3)2CH (2),(CH3)3SiCH2 (3),C2H5 (4),(CH3)2CHCH2 (5)]allows the high yield and stereoselective liberationof the corresponding tritertiary macrocycles[syn,syn-R3L, R =(CH3)2CH (6),(CH3)3SiCH2 (7),C2H5 (8),(CH3)2CHCH2 (9)] in good yield (75-80%) bydigestion in strong base. This method fails for the parenttrisecondarymacrocycle (H3L) and also for the intermediate Mo(II)salts,[(R3L)Mo(CO)3X]A-[X = halide, A- = halide,BPh4 (1)]. Addition of halogen to(H3L)Cr(CO)3 gives rise to the newblue-violet complexes(H3L)Cr(CO)2X2[X = Cl2 (11), Br2(12)]. Paramagnetic susceptibilities indicate that11 and 12 are low-spin d4 sixcoordinatedicarbonyl halo-halide complexes of the type[(H3L)Cr(CO)2X]X. In thiscase, the trisecondary 1,5,9-triphosphacyclododecane (H3L, 13) may beliberated stereoselectively and in reasonable yield (60-70%)from11 or 12. The macrocycles may alternativelybe liberated from the Mo(II) dihalo complexes by action ofCN-.The free trisecondary macrocycle can be alkylatednonstereoselectively to give the tritertiary macrocycles[syn,anti-R3L; R = CH3 (24),C2H5 (8b),(CH3)3C (25)]. The inversionof phosphorus in the syn,syn isomer 8 toitssyn,anti analogue, 8b, was shown to be slowat 156 
C. Exhaustive oxidation of the Mo(0) macrocyclecomplexeswith H2O2 or O3 results inliberation of the corresponding macrocycle trioxides in good yield.All free macrocycles(and oxides) have been characterized by spectroscopic methods and asthe hydrochlorides for selected ligands.
C. Exhaustive oxidation of the Mo(0) macrocyclecomplexeswith H2O2 or O3 results inliberation of the corresponding macrocycle trioxides in good yield.All free macrocycles(and oxides) have been characterized by spectroscopic methods and asthe hydrochlorides for selected ligands.