FORMATION OF ANTIFERROMAGNETIC HETERONUCLEAR THIOLATE-BRIDGED AND SULFIDE-BRIDGED COMPLEXES .3. PREPARATION, MAGNETIC-PROPERTIES, AND STRUCTURES OF CR2W CLUSTERS AND NITROSYLCHROMIUM COMPLEXES

The reaction of the polymeric [W(NO)(2)Cl-2](n) (8) with the antiferro magnetic complex CP2Cr2(mu-SCMe(3))(2)(mu-S) (3) (benzene, 40 degrees C) leads to formation of the adduct [Cp(2)Cr(2)(mu-SCMe(3))(2)(mu(3)-S )]W-2(NO)(2)Cl-2 (9). Thermolysis of 9 initiates both cluster formatio n and nitrosylation of the binuclear dichromium unit yielding the anti ferromagnetic triangular clusters Cp(2)Cr(2)(mu(3)-S)(2)(mu-SCMe(3))(2 )W(NO)(2) (11, -2J = 272 cm(-1), W-Cr = 2 x 3.088(3) Angstrom, Cr-Cr = 3.025(4) Angstrom), Cp(2)Cr(2)(mu(3)-S)(2)(mu-SCMe(3))(2)W(NO)Cl (12, -2J = 270 cm(-1), W-Cr = 2.843(3)-2.889(3) Angstrom, Cr-Cr = 3.036(4) and 3.068(4) Angstrom), and the known species CP2Cr2(mu(3)-S)(2)(mu-S CMe(3))(2)W(NO)(SCMe(3)) (2) and furthermore the diamagnetic nitrosyl- containing chromium complexes Cp(2)Cr(2)(NO)(2)(mu-SCMe(3))(mu-Cl) (16 , Cr-Cr = 2.959(2) Angstrom), Cp(4)Cr(4)(NO)(3)Cl(mu SCMe(3))(2)(mu(4) -S-2) (17, Cr-Cr = 2.968(2) Angstrom, S-S = 2.107(3) Angstrom), and Cp (2)Cr(2)(No)(2)(mu-SCMe(3))-(mu-SSCMe(3)) (15). Compounds 15, 16, and Cp(2)Cr(2)(NO)(Cl)(mu-SCMe(3))(2) (18, Cr-Cr = 3.071(8)-3.116(8) Angst rom) were also prepared by the reaction of 3 with NOCl. In the presenc e of moisture the intended conversions to 3 and 8 led to insoluble pow ders containing no NO groups. Upon addition of PPr3 to this mixture a small amount of the paramagnetic ionic complex [WCl(H)(2)(H2O)(PPr3)(2 )] [CpCrCl(3)] (10, W-Cl = 2.296(2) Angstrom, W-P = 2.357(2) Angstrom, W-H = 1.50(3) and 1.63(3) Angstrom) is produced. 10-12 and 16-18 were characterized by X-ray studies: 10.MeCN, space group P2(1)/m, a = 10. 679(5) Angstrom, b = 12.967(5) Angstrom, c = 13.678(5) Angstrom, beta = 111.97(2)degrees, Z = 2, V = 1756.6(12) Angstrom(3); 11, space group C2/c, a = 21.741(13) Angstrom, b = 9.932(4) Angstrom, c = 14.868(10) Angstrom, beta = 129.01(2)degrees, Z = 4, V = 2495(2) Angstrom(3); 12. 0.25CH(2)Cl(2), space group P2(1)/n, a = 9.495(5) Angstrom, b = 32.89( 2), c = 17.451(8) Angstrom, beta = 90.76(2)degrees, Z = 8 (two indepen dent molecules), V = 5449(5) Angstrom(3); 16, space group P2(1)2(1)2(1 ), a = 6.533(3) Angstrom, b = 9.390(3) Angstrom, c = 29.206(13) Angstr om, Z = 4, V = 1791.7(13) Angstrom(3); 17.C6H6, space group P1, a = 9. 619(5) Angstrom, b = 10.320(5) Angstrom, c = 11.799(6) Angstrom, alpha = 106.32(2)degrees, beta = 108.45(2)degrees, gamma = 102.75(2)degrees , Z = 1, V = 1002.8(9) Angstrom(3); 18, space group P2(1)/n, a = 16.31 1(11) Angstrom, b = 16.644(11) Angstrom, c = 28.869(17) Angstrom, beta = 95.85(2)degrees, Z = 12 (three independent molecules), V = 6859(5) Angstrom(3).