16800-44-5Relevant academic research and scientific papers
Transition metal complexes with sulfur ligands. 97. Coordinatively and electronically unsaturated and saturated Cr0, Mo0, and W0 dithiolate complexes of the type [M(CO)3('S2')]2- and [M2(CO)7('S2')]2- {'S2'2- = S2 ...
Sellmann, Dieter,Wille, Monika,Knoch, Falk
, p. 2534 - 2543 (2008/10/08)
Full title: Transition metal complexes with sulfur ligands. 97. Coordinatively and electronically unsaturated and saturated Cr0, Mo0, and W0 dithiolate complexes of the type [M(CO)3('S2')]2- and [M2(CO)7('S2')]2- {'S2'2- = S2C6R42- (R = H, Cl, Me); S2C2H42-}. Reactions of [Cr(CO)3(MeCN)3] with S2C6R42- (R = Cl, Me) yielded coordinatively and electronically unsaturated [Cr(CO)3(S2C6Cl4)]2-, [1]2-, and [Cr(CO)3(S2C6Me4)]2-, [2]2-. X-ray structure determination proved the Cr0 center of [1]2- to be five-coordinate and surrounded in a distorted trigonal bipyramid by three carbon and two sulfur donors. The distances indicate the double-bond character of the Cr-S bonds (231.8 pm) suggesting that the S2C6Cl42- ligand acts as σ-π donor such that the Cr0 center achieves a formal 18 e- configuration. The reaction of CrCl2 with S2C6H42- led to [Cr(S2C6H4)2]2-, [12]2-, which is shown by X-ray structure determination to have a four-coordinate CrII center, the short Cr-S bonds (236.2 pm) exhibiting partial double-bond character. When reacted with CO, [1]2- and [2]2- yielded coordinatively and electronically saturated [Cr(CO)4(S2C6R4)]2- (R = Cl, [3]2-; R = Me, [4]2-). The X-ray structure determination of [3]2- showed that the Cr center is six-coordinate and surrounded pseudooctahedrally by four carbon and two cis sulfur donors. The average Cr-S distance (242.0 pm) is significantly longer than that in [1]2-. Reactions of [M(CO)3('S2')]2- (M = Cr, Mo, W; 'S2' = S2C2H4, S2C6R4) with [M(CO)4] complexes (M = Cr, Mo, W) yielded the dinuclear [Cr2(CO)7(S2C2H4)] 2-, [5]2-, [Cr2(CO)7(S2C6H10)] 2-, [6]2-, [Mo2(CO)7(S2C2H4)] 2-, [7]2-, [W2(CO)7(S2C2H4)] 2-, [8]2-, and [Cr2(CO)7(S2C6R4)] 2- (R = H, [9]2-; R = Cl, [10]2-; R = Me, [11]2-). X-ray structure determinations of [5]2-, [6]2-, [7]2-, and [10]2- revealed that the metal centers each are surrounded pseudooctahedrally by four carbon and two sulfur donors, the sulfur donors, and one CO group bridging two [M(CO)3] fragments. In addition, the metal centers are connected by M-M single bonds and reach 18 e- configurations. Accordingly, the M-S bonds exhibit single-bond character ([5]2-, dCr-S = 241.9 pm; [6]2-, dCr-S = 242.9 pm; [7]2-, dMo-S = 256.5 pm; [10]2-, dCr-S = 243.5 pm). Crystal data for (NEt4)2[Cr(CO)3(S2C 6Cl4)]: monoclinic space group P21/c, a = 1518.5(15) pm, b = 1355.8(8) pm, c = 1564.2(11) pm, β = 100.41(7)°, Z = 4, Rw = 6.6/5.1%. Crystal data for (NEt4)2[Cr(CO)4(S2C 6Cl4)]: orthorhombic space group Pca21, a = 1520.2(4) pm, b = 2830.2(5) pm, c = 1505.4(4) pm, Z = 8, R/Rw = 4.0/4.0%. Crystal data for (NEt4)2[Cr(S2C6H4) 2]: monoclinic space group P21/n, a = 1746.6(6) pm, b = 1203.4(5) pm, c = 1748.3(6) pm, β = 119.82(3) °, Z = 4, R/Rw = 6.8/4.8%. Crystal data for (PPh4)2[Cr2(CO)7(S2C 2H4)]: monoclinic space group C2/c, a = 1887.0(9) pm, b = 1118.4(3) pm, c = 2534.6(1) pm, β = 110.67(3) °, Z = 4, R/Rw = 8.3/6.4%. Crystal data for (NEt4)2[Cr2(CO)7(S2C 6H10)]·0.55MeOH: monoclinic space group C2/c, a = 2384.0(7) pm, b = 893.2(3) pm, c = 3421.0(15) pm, β = 93.91(3) °, Z = 8, R/Rw = 8.0/6.5%. Crystal data for (PPh4)2[Mo2(CO)7(S2C 2H4)]·THF: trigonal space group P31, a = b = 1103.4(1) pm, c = 3949.5(11) pm, Z = 3, R/Rw = 6.5/4.5%. Crystal data for (PPh4)2[Cr2(CO)7(S2C 6Cl4)]·MeCN: monoclinic space group P21/c, a = 1666.2(8) pm, b = 1597.6(10) pm, c = 2263.4(10) pm, β = 90.22(4) °, Z = 4, R/Rw = 5.5/4.3%.
Hydroxycarbene complexes from paramagnetic acylmetals. Electrochemistry of benzoylchromium(0) and -tungsten(0) carbonyls
Klingler,Huffman,Kochi
, p. 34 - 40 (2008/10/08)
The group 6 acylmetal(0) anions RCOCr(CO)5- and RCOW(CO)5- yield paramagnetic acylchromium(I) and -tungsten(I) species upon anodic oxidation. Ion-pairing effects with various cations are shown by the shifts of t
