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The photo-induced decarbonylation of Cp'Cr(NO)(CO)(2) (1a) in MeCN solution in the presence of R2E2 (E = S, Se; R = Me, Ph) leads to the formation of chalcogenolato-bridged binuclear complexes Cp-2'Cr-2(NO)(2)(mu -ER)(2) [E = S; R = Me (2a), Ph (3a); E = Se, R = Me (4a), Ph (5a)] while reactions between Cp'M(NO)(CO)(2) [M = Mo (1b), W (1c)] and Ph2E2 (E = S, Se) result in mononuclear complexes Cp'M(NO)(EPh)(2) [M = Mo; E = S (9b), Se (10b); M = W, E = S (11c), Se (12c)]. The corresponding reactions of (1b) with Me2E2 (E = S, Se) yielded both mono and binuclear complexes: Cp'Mo(NO)(SeMe)(2) (8b), Cp-2'Mo-2(NO)(2)(mu -EMe)(2) [E = S (6b), Se (7b)]. The new complexes have been characterized by i.r., H-1-, C-13-n.m.r. spectra and by electron-impact mass spectrometry.