TY - JOUR
T1 - Synthesis, characterization, and reactivity of PPN[Cr(CO)4(NO)]
AU - Mantell, Daniel R.
AU - Gladfelter, Wayne L.
N1 - Funding Information:
This research was supported by a grant from the National Science Foundation.
PY - 1988/6/21
Y1 - 1988/6/21
N2 - The new nitrosyl carbonylmetalate PPN[Cr(CO)4(NO)] has been synthesized from Cr(CO)6 and PPN(NO2) in THF (PPN = bis(triphenylphosphine)iminium cation). The material was characterized by infrared and 15N NMR spectroscopy and by elemental analysis, which demonstrated it has the same structure as Mn(CO)4(NO). Kinetic experiments show the reaction to be first order in both chromium and nitrite with k = 0.25 ± 0.05 M-1 sec-1 at 58.60 ± 0.05°C. A mechanism consistent with this and related results is discussed. Metalcarbon, metalhydrogen, and metalmetal bonds have been formed by the reactions of PPN[Cr(CO)4(NO)] with eletrophiles (CF3SO3CH3, CF3SO3H, Ph3SnCl). With the labile complexes, M(CO)5(THF) (M = Cr, Mo and W), PPN[Cr(CO)4(NO)] produces the homo- and hetero-dinuclear complexes PPN[CrM(CO)9(NO)] (M = Cr, Mo and W).
AB - The new nitrosyl carbonylmetalate PPN[Cr(CO)4(NO)] has been synthesized from Cr(CO)6 and PPN(NO2) in THF (PPN = bis(triphenylphosphine)iminium cation). The material was characterized by infrared and 15N NMR spectroscopy and by elemental analysis, which demonstrated it has the same structure as Mn(CO)4(NO). Kinetic experiments show the reaction to be first order in both chromium and nitrite with k = 0.25 ± 0.05 M-1 sec-1 at 58.60 ± 0.05°C. A mechanism consistent with this and related results is discussed. Metalcarbon, metalhydrogen, and metalmetal bonds have been formed by the reactions of PPN[Cr(CO)4(NO)] with eletrophiles (CF3SO3CH3, CF3SO3H, Ph3SnCl). With the labile complexes, M(CO)5(THF) (M = Cr, Mo and W), PPN[Cr(CO)4(NO)] produces the homo- and hetero-dinuclear complexes PPN[CrM(CO)9(NO)] (M = Cr, Mo and W).
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U2 - 10.1016/0022-328X(88)80157-8
DO - 10.1016/0022-328X(88)80157-8
M3 - Article
AN - SCOPUS:0000863629
SN - 0022-328X
VL - 347
SP - 333
EP - 342
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 3
ER -