Synthese und strukturelle charakterisierung von übergangsmetallsulfidclustern mit Cp★Mo- (Cp★ = C5Me5), CuCl- und Fe(NO)-baugruppen

Abstract

The reaction of CP*~M~S, In a metathetical reaction with NaSPh, 3 gives Cp*zMo$u,(SPh),S, .

Synthesis, crystal structures and third-order nonlinear optical properties of a new family of double incomplete cubane-like clusters [(η5-C5Me5)2Mo2(μ3-S)3SCu2X(μ-X)]2 (X=Cl−, Br−, SCN−) and cubane-like clusters [(η5-C5Me5)2Mo2(μ3-S)4(CuX)2] (X=Br−, SCN−, CN−)

“…Each Cu atom has a distorted tetrahedral coordination geometry. The mean MoÁ Á ÁCu contact, Mo-l 3 -S and Cu-l 3 -S bond lengths are comparable to those found in other Mo 2 S 4 Cu 2 cubane-like clusters such as [(dtc) 2 Mo 2 (l 3 -S) 4 (CuBr) 2 ] [43] and [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 4 (CuX) 2 ] (X=Cl, I) [40,41]. The mean MoÁ Á ÁMo contact is longer than that in [(dtc) 2 Mo 2 (l 3 -S) 4 (CuBr) 2 ], but comparable to those in [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 4 (CuX) 2 ] (X = Cl, I).…”

“…1). Relative to the bands at 338 and 448 nm (1) [40], those at 350 and 491 nm (2), 393 and 474 nm (3), 352 and 491 nm (4), 387 and 468 nm (5), 469 nm (6), and 456 nm (7) are red-shifted, and they are probably dominated by the S ! Mo(V) charge-transfer transitions of [(g 5 -C 5 Me 5 ) 2 Mo 2 S 4 ] moiety [41,46].…”

“…As mentioned earlier in this paper, 6 has very low yield and thus we did not measure its NLO properties. On the other hand, we included the known cubane-like cluster [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 3 S(CuCl) 2 ] [40] in the measurement of third-order NLO properties of this series. As shown in Fig.…”

“…For example, reactions of a solution containing trans-[(g 5 -C 5 Me 5 ) 2 Mo 2 (l-S) 2 S 2 ] (1) with 2 equiv. of CuCl in toluene gave rise to a cubane-like cluster [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 4 (CuCl) 2 ] [40].…”

“…However, only a few reactions are involved in the utilization of the disulfido-bridged dimolybdenum clusters [Cp 0 2 Mo 2 S 4 ] (Cp 0 = g 5 -C 5 H 5 , g 5 -C 5 H 4 Me or g 5 -C 5 Me 5 ) [40,41]. For example, reactions of a solution containing trans-[(g 5 -C 5 Me 5 ) 2 Mo 2 (l-S) 2 S 2 ] (1) with 2 equiv.…”