From the reactions between M-2(T(i)PB())4 and HO2CC6H5-eta(6)-Cr(CO)(3) (2 equiv), the title compounds trans-M-2((TPB)-P-i)(2)[O2CC6H5-eta(6)-Cr(CO)(3)](2), where M = Mo or W, and (TPB)-P-i = 2,4,6-triisopropylbenzoate have been prepared and characterized. Compound I (M = Mo) was characterized by a single crystal X-ray structural determination which revealed a centrosymmetric MoMo quadruply bonded molecule. Compound I is red and the tungsten complex II is blue as a result of intense metal-to-ligand charge transfer (MLCT), which is principally M-2 delta to benzoate pi* with some chromium t(2g) participation, according to calculations employing density functional theory. Compound I shows dual emission from S-1 and T-1 states that are assigned (MLCT)-M-1 and (3) MoMo delta delta*, respectively. Both complexes have been studied by time-resolved infrared spectroscopy (TRIR) in the region of the carbonyl stretching frequency. Compound II displays a shift of nu(CO) to lower energy in both the (MLCT)-M-1 and (MLCT)-M-3 states in THF, while I in CH2Cl2 shows nu(CO) bands shifted to both higher and lower energy. We attribute the shift to higher energy seen for I to a Cr t(2g) to benzoate pi* transition which mixes with the Mo-2 delta to benzoate charge transfer upon excitation at 514 nm. In THF compound I undergoes a reversible photodissociation, potentially due to CO loss. Based on the TRIR of the carbonyl vibrations, it is proposed that the MLCT states are delocalized over both benzoate Cr(CO)(3) groups, as supported by calculations.