REACTIONS OF METAL METAL AND METAL-CARBON MULTIPLE BONDS WITH 2H-AZIRINES, 1,3-DIPOLAR REAGENTS - STRUCTURES OF CP2M2(CO)4(NC(AR)=CME2) (AR=ARYL M=MO, W) AND (CO)5W-N(=CPH(OME))(C(PH)=CME2)

被引：18
|
作者：
CURTIS, MD [1 ]
HAY, MS [1 ]
BUTLER, WM [1 ]
KAMPF, J [1 ]
RHEINGOLD, AL [1 ]
HAGGERTY, BS [1 ]
机构：
[1] UNIV DELAWARE,DEPT CHEM,NEWARK,DE 19716
来源：
ORGANOMETALLICS | 1992年 / 11卷 / 08期
关键词：
D O I：
10.1021/om00044a031
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reactions of compounds (C5R5)2M2(CO)4(M=M) (R = Me, H; M = Mo, W) and W2(OBu(t))6(W=W) with 2,2-dimethyl-3-aryl-2H-azirines lead to the vinylimido adducts Cp*2W2(CO)4(NC(Ar)=CMe2) (Ar = 4-tert-butylphenyl; 6), CP*2Mo2(CO)4(NC(Ar)=CMe2) (Ar = 4-tert-butylphenyl, 8a; Ar = phenyl, 8b), CP2Mo2(CO)4(NC(Ph)=CMe2) (7), and W2(O(t)Bu)6(NC(Ar)=CMe2)2 (Ar = 4-tert-butylphenyl, 9b; Ar = phenyl, 9a). Complex 7 exists in two isomeric forms that are in dynamic equilibrium. With the carbene complexes (CO)5W=C(OMe)Ph and [Cp(CO)2Fe=C(OMe)Me]X (X = BF4, PF6), the vinylimidate complexes (CO)5WN(=C(OMe)Ph)(C(Ph)=CMe2) (11) and CP(CO)2FeN(=C(OMe)Me)(C(Ar)=CMe2) (13) are produced. Air oxidation of 11 releases the imidate ligand. In these reactions, the 2H-azirine is behaving as a masked vinylnitrene rather than as a nitrile ylide. The structures of 6, 8b, and 11 are determined: 6, a = 8.2120 (2) angstrom, b = 11.2370 (3) angstrom, c = 15.5170 (4) angstrom, alpha = 71.51 (2)-degrees, beta = 84.24 (2)-degrees, gamma = 81.71 (2)-degrees, V = 1341.5 angstrom3, Z = 2, space group P1BAR (triclinic), R = 0.0360, R(w) = 0.0399 based on 5050 reflections with F(o) greater-than-or-equal-to 3-sigma(F); 8b, a = 17.490 (6) angstrom, b = 8.973 (3) angstrom, c = 22.023 (6) angstrom, beta = 109.09 (2)-degrees, V = 3266 (2) angstrom3, Z = 4, space group Cc (monoclinic), R = 0.0280, R(w) = 0.0214 based on 2455 reflections with F(o) greater-than-or-equal-to 3-sigma(F); 11, a = 12.141 (9) angstrom, b = 11.770 (5) angstrom, c = 16.91 (2) angstrom, beta = 107.02 (6)-degrees, V = 2310 (3) angstrom3, Z = 4, space group P2(1)/n (monoclinic), R = 0.0612, R(w) = 0.0847 based on 2416 reflections with F(o) greater-than-or-equal-to 3-sigma(F). The structure of 6 is Cp(CO)(NR)W-W(CO)3Cp with CO semibridging, but 8b has a structure with two nearly symmetrical CO bridges: Cp*(NR)Mo(mu-CO)2Mo(CO)2Cp*(Mo-Mo) (R = C(Ar)CMe2).
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页码：2884 / 2892
页数：9
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