Dissociative CO Photosubstitution in M(CO)₄(1,4-diazabutadiene) Complexes (M = W, Mo) by an Olefin Affording Novel <i>f</i><i>ac</i>-M(CO)₃(1,4-diazabutadiene)(η²-olefin) Derivatives

Abstract

Photolysis of M(CO) 4 (iprop-dab) ( 1, M = W; 2, M = Mo; iprop-dab = 1,4-diisopropyl-1,4-diazabuta-1,3-diene) in the presence of ( E )-cyclooctene (eco) afforded high yields of the unprecedented olefin-substituted derivatives fac -M(CO) 3 (iprop-dab)(η 2 -eco) ( 3, M = W, 93%; 4, M = Mo, 84%), which were comprehensively characterized by IR, UV−vis, and NMR spectroscopy and by an X-ray diffraction structure analysis of 3 . Quantum yield measurements at 254, 302, 365, and 405 nm revealed a gradual decrease from Φ ≈ 0.1 to 0.02 and then a sharp drop to 0.001 at 548 nm (CTML excitation). Irradiation of 2 in low-temperature matrices, as monitored by means of IR spectroscopy in the ν(CO) region, was shown to yield fac -Mo(CO) 3 (iprop-dab) ( 5, in Ar or CO-doped Ar), fac -Mo(CO) 3 ( 13 CO)(iprop-dab) (in 13 CO-doped Ar), and fac -Mo(CO) 3 (N 2 )(iprop-dab) ( 6, in N 2 ), thereby establishing that a vacant axial coordination site is created by photolytic CO dissociation, with wavelength-dependent efficiency. The involvement of the (solvated) fragment fac -M(CO) 3 (iprop-dab) as a key intermediate in the solution photochemistry of M(CO) 4 (iprop-dab) was substantiated by laser flash photolysis of 2 in combination with time-resolved IR and UV−vis spectroscopy. 13 CO-enriched samples of 1 and 2 (specifically monolabeled) as well as 3, 5, and 6 (partially labeled) were used for gathering complementary ν(CO) data as a basis for energy-factored CO force field analyses. The response of the low-energy CTML electronic transitions to the loss of CO and its replacement by the olefin or N 2 ligand is discussed in terms of ligand-dependent metal d(π) level stabilization.