TY - JOUR
T1 - Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen. XIII. Aufbau, strukturchemie und reaktivität von schwefel- und selen-brücken in zweikernigen organochrom-komplexen
AU - Herrmann, Wolfgang A.
AU - Rohrmann, Jürgen
AU - Nöth, Heinrich
AU - Nanila, Ch K.
AU - Bernal, Ivan
AU - Draux, Madelein
PY - 1985/4/2
Y1 - 1985/4/2
N2 - Novel dinuclear organochromium complexes exhibiting bare sulfur and selenium bridging ligands are accessible by treating trithiazyl trichloride, diselenium dichloride, or sodium selenite/hydrochloric acid, respectively, with the ionic complex species M+ [(η5-C5R5)Cr(CO)3]- (1: M = K, R = CH3 6a: M = Na, R = H). The monoselenido and diselenido complexes (μ-Se)[(η5-C5H5)Cr(CO)2]2 (7) and (μ-Se2)[η5-C5H5)Cr(CO)2]2 (8) are also obtained by treatment of [(η5-C5H5)Cr(CO)3]2 with equimolar or excess amounts of black selenium, respectively (yield 98%). The thio- and selenoformaldehyde complexes (μ, η2-XCH2[η5-C5R5)Cr(CO)3]2 (5: X = S, R = CH3; 9a: X = Se, R = H) are formed when diazomethane is added to the reactive precursor compounds (μ, η1: η2-S2)[(η5-C5Me5)2Cr2(CO)5] (2) and (μ-Se2)[η5-C5H5Cr(CO)2]2 (8), respectively; this synthetic methodology yields the selenoacetone complex (μ, η2-SeCMe2)[(η5-C5H5)Cr(CO)2]2 (9b), with compound 7 and 2-diazopropane acting as starting compounds in this case. The same products are obtained in a much better way if the respective diazoalkanes are treated with the monoselenido complex (μ-Se)[(η5-C5H5)Cr(CO)2]2 (7) having chromium-selenium triple bonds; in contrast, the μ-sulfido complex 3, structurally analogous to 7, is unreactive in the presence of diazoalkanes. The μ, η2: η2-disulfido complex 4 exhibits a symmetrical four-membered Cr2S2 core which, according to a single-crystal X-ray structure determination, is folded by 120° along the very short sulfur-sulfur bond (199.5(2) pm), thus describing a butterfly-type geometry; bonding interaction between the two metal atoms is not present (d(Cr ⋯ Cr) 377 pm). In agreement with the EAN rule, the μ-selenido complex 7 displays a linear coordinated selenium bridge (X-ray structure) bonded to both organochromium fragments via cumulated triple bonds (d(CiSe) 220.6(1), 221.1(1) pm). The relative orientations of the (η5-C5H5)Cr(CO)2 structures in the crystal yield an anticlinal conformation of the molecule.
AB - Novel dinuclear organochromium complexes exhibiting bare sulfur and selenium bridging ligands are accessible by treating trithiazyl trichloride, diselenium dichloride, or sodium selenite/hydrochloric acid, respectively, with the ionic complex species M+ [(η5-C5R5)Cr(CO)3]- (1: M = K, R = CH3 6a: M = Na, R = H). The monoselenido and diselenido complexes (μ-Se)[(η5-C5H5)Cr(CO)2]2 (7) and (μ-Se2)[η5-C5H5)Cr(CO)2]2 (8) are also obtained by treatment of [(η5-C5H5)Cr(CO)3]2 with equimolar or excess amounts of black selenium, respectively (yield 98%). The thio- and selenoformaldehyde complexes (μ, η2-XCH2[η5-C5R5)Cr(CO)3]2 (5: X = S, R = CH3; 9a: X = Se, R = H) are formed when diazomethane is added to the reactive precursor compounds (μ, η1: η2-S2)[(η5-C5Me5)2Cr2(CO)5] (2) and (μ-Se2)[η5-C5H5Cr(CO)2]2 (8), respectively; this synthetic methodology yields the selenoacetone complex (μ, η2-SeCMe2)[(η5-C5H5)Cr(CO)2]2 (9b), with compound 7 and 2-diazopropane acting as starting compounds in this case. The same products are obtained in a much better way if the respective diazoalkanes are treated with the monoselenido complex (μ-Se)[(η5-C5H5)Cr(CO)2]2 (7) having chromium-selenium triple bonds; in contrast, the μ-sulfido complex 3, structurally analogous to 7, is unreactive in the presence of diazoalkanes. The μ, η2: η2-disulfido complex 4 exhibits a symmetrical four-membered Cr2S2 core which, according to a single-crystal X-ray structure determination, is folded by 120° along the very short sulfur-sulfur bond (199.5(2) pm), thus describing a butterfly-type geometry; bonding interaction between the two metal atoms is not present (d(Cr ⋯ Cr) 377 pm). In agreement with the EAN rule, the μ-selenido complex 7 displays a linear coordinated selenium bridge (X-ray structure) bonded to both organochromium fragments via cumulated triple bonds (d(CiSe) 220.6(1), 221.1(1) pm). The relative orientations of the (η5-C5H5)Cr(CO)2 structures in the crystal yield an anticlinal conformation of the molecule.
UR - http://www.scopus.com/inward/record.url?scp=0000475861&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(85)87212-0
DO - 10.1016/0022-328X(85)87212-0
M3 - Artikel
AN - SCOPUS:0000475861
SN - 0022-328X
VL - 284
SP - 189
EP - 211
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 2
ER -