%0 Generic
%A Rozenel, Sergio S.
%A Padilla, Rosa
%A Arnold, John
%D 2016
%T Chemistry
of Reduced Monomeric and Dimeric Cobalt Complexes Supported by a PNP
Pincer Ligand
%U https://acs.figshare.com/articles/dataset/Chemistry_of_Reduced_Monomeric_and_Dimeric_Cobalt_Complexes_Supported_by_a_PNP_Pincer_Ligand/2369653
%R 10.1021/ic4018882.s003
%2 https://acs.figshare.com/ndownloader/files/4009147
%K PNP ligand
%K PNP Pincer LigandThe reduction chemistry
%K AgBPh 4
%K electron count
%K 15 electrons
%K HN
%K Monomeric square
%K Complex 3
%K Dimeric Cobalt Complexes
%K KC 8
%K cobalt complexes
%K HPNP
%K NMR
%K oxidative addition
%K 5 activates
%K Reduced Monomeric
%K species 7
%X The
reduction chemistry of cobalt complexes with HPNP (HPNP = HN(CH2CH2PiPr2)2) as a supporting ligand is described. Reaction of [(HPNP)CoCl2] (1) with n-BuLi generated
both the deprotonated Co(II) species [(PNP)CoCl] (2)
along with the Co(I) complex [(HPNP)CoCl] (3). Products
resulting from reduction of 2 with KC8 vary
depending upon the atmosphere under which the reduction is performed.
Monomeric square planar [(PNP)CoN2] (4) is
obtained under dinitrogen, whereas dimeric [(PNP)Co]2 (5) is formed under argon. Over time, 5 activates
a C–H bond in the PNP ligand to form the species [Co(H)(μ-PNP)(μ-iPr2PCH2CH2NCHCH2PiPr2)Co]
(6). We also observed the oxidative addition of H–Si
bond to complex 3 to form [(HPNP)CoCl(H)SiH2Ph] (7). 1H NMR studies showed that species 7 is in equilibrium with 3 and silane in solution.
Complex 3 can be oxidized with AgBPh4 to generate
{(HPNP)CoCl}BPh4 (8), a square planar species
with a formal electron count of 15 electrons.
%I ACS Publications