71564-17-5Relevant articles and documents
THE GENERATION IN SOLID CO OF THE RADICAL Mn(CO)5
Church, S. P.,Poliakoff, M.,Timney, J. A.,Turner, J. J.
, p. 159 - 162 (1982)
The radical Mn(CO)5 is generated by the photolysis of HMn(CO)5 in a low temperature solid CO matrix.It is characterized by IR spectroscopy, including isotopic studies, and it is shown to have a visible absorption band at ca. 800 nm, close to that assigned to Mn(CO)5 in room-temperature studies.
Properties and dynamics of the σ(M′-Re) π* excited state of photoreactive dinuclear LnM′-Re(CO) 3 (α-diimine) (LnM′ = Ph3Sn, (CO)5Mn, (CO)5Re; α-diimine = bpy′, iPr-PyCa, iPr-DAB) complexes studied by time-resolved emission and absorption spectroscopies
Rossenaar, Brenda D.,Lindsay, Elspeth,Stufkens, Derk J.,Vl?ek Jr., Antonín
, p. 5 - 14 (2008/10/08)
The photophysics and photochemistry of the metal-metal bonded complexes LnM′Re(CO)3(α-diimine) (LnM′ = Ph3Sn, (CO)5Re, (CO)5Mn; α-diimine = bpy′, iPr-PyCa, iPr-DAB) have been studied. According to the time-resolved emission (80 K) and absorption (room temperature) spectra, the lowest excited state has a 3σ (M′-Re) π* character. It is a bound state, which can only be populated by surface crossing from optically excited MLCT states. Homolysis of the metal-metal bond from the σπ* state is promoted by nucleophilic and chlorinated solvents. Exceptional in this respect is the complex Ph3SnRe(CO)3(bpy′), which is nearly photostable in non-chlorinated solvents. The lifetime of the 3σπ* state decreases in the order α-diimine = bpy′ > iPr-PyCa > iPr-DAB > pAn-DAB. This trend is mainly determined by the energy gap law. The LnM′ dependence is more complicated because of an additional deactivating effect of an excited state distortion which depends on LnM′. At 80 K, the lifetime is determined by the weak coupling to the ground state; at room temperature by dissociation of M′-Re (with the exception of Sn-Re).
Comparative matrix isolation and time-resolved infrared studies on the photochemistry of MnRe(CO)10 and Re2(CO)10: Evidence for CO-bridged MnRe(CO)9
Firth, Stephen,Hodges, P. Michael,Poliakoff, Martyn,Turner, James J.
, p. 4608 - 4610 (2008/10/08)
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