TY - JOUR
T1 - Heats of reaction of HMo(CO)3C5H5 with CCl4 and CBr4 and of NaMo(CO)3C5H5 with I2 and CH3. Solution thermochemical study of the MoX bond for X = H, Cl, Br, I and CH3
AU - Nolan, Steven P.
AU - De La Vega, Ramón López
AU - Hoff, Carl D.
PY - 1986/11/11
Y1 - 1986/11/11
N2 - The heats of reaction of HMo(CO)3C5H5 with CX4 (X = Cl, Br) producing XMo(CO)3C5H5 have been measured by solution calorimetry and are -31.8±0.9 and -34.4±2.0 kcal/mole, respectively. The heats of reaction of NaMo(CO)3C5H5 with I2 and CH3I producing IMo(CO)3C5H5 and H3CMo(CO)3C5H5 are -32.3± 1.3 and -7.7± 0.3 kcal/mole. Oxidation with Br2CCl4 yielding Br3Mo(CO)2C5H5 was measured for the following complexes: (C5H5(CO)3Mo)2, (-92.0±1.0 kcal/mole), BrMo(CO)3C5H5 (-24.9± 2.0 kcal/mole) and HMo(CO)3C5H5 (-60.7± 2.0 kcal/mole). These and other data are used to calculate the Mo-X bond strength for X = H, Cl, Br, I, and CH3. These bond strength estimates are compared to those reported for X2Mo(C5H5)2. Iodination of H3CMo(CO)3C5H5, reported in the literature to yield CH3I and IMo(CO)3C5H5, actually produces CH3C(O)I and I3Mo(CO)2C5H5.
AB - The heats of reaction of HMo(CO)3C5H5 with CX4 (X = Cl, Br) producing XMo(CO)3C5H5 have been measured by solution calorimetry and are -31.8±0.9 and -34.4±2.0 kcal/mole, respectively. The heats of reaction of NaMo(CO)3C5H5 with I2 and CH3I producing IMo(CO)3C5H5 and H3CMo(CO)3C5H5 are -32.3± 1.3 and -7.7± 0.3 kcal/mole. Oxidation with Br2CCl4 yielding Br3Mo(CO)2C5H5 was measured for the following complexes: (C5H5(CO)3Mo)2, (-92.0±1.0 kcal/mole), BrMo(CO)3C5H5 (-24.9± 2.0 kcal/mole) and HMo(CO)3C5H5 (-60.7± 2.0 kcal/mole). These and other data are used to calculate the Mo-X bond strength for X = H, Cl, Br, I, and CH3. These bond strength estimates are compared to those reported for X2Mo(C5H5)2. Iodination of H3CMo(CO)3C5H5, reported in the literature to yield CH3I and IMo(CO)3C5H5, actually produces CH3C(O)I and I3Mo(CO)2C5H5.
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U2 - 10.1016/0022-328X(86)80437-5
DO - 10.1016/0022-328X(86)80437-5
M3 - Article
AN - SCOPUS:0037537517
VL - 315
SP - 187
EP - 199
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 2
ER -