TY - JOUR
T1 - Half-sandwich iron(II) complexes with protic acyclic diaminocarbene ligands
T2 - Synthesis, deprotonation and metalation reactions
AU - Gomez-Ruiz, Fernando Javier
AU - Garcia , Lucia
AU - Vivanco, Marilín
AU - Sol, Daniel
AU - García-Granda, Santiago
PY - 2017/8/21
Y1 - 2017/8/21
N2 - A variety of half-sandwich iron(ii) complexes with diprotic acyclic diaminocarbene ligands (pADCs) have been obtained by reaction of the cationic complexes [Fe(Cp)(CO)2(CNR)]+ and [Fe(Cp)(CO)(CNR)2]+ with methylamine, and their acid-base behaviour was studied, revealing an easy reversible deprotonation reaction of both N-H moieties of the carbene ligands. The deprotonation process is frequently followed by a nucleophilic attack of the nitrogen atom on a vicinal carbonyl or isocyanide ligand, affording the corresponding metallacycles. Metalation of one or two N-H groups of the pADC ligands can be accomplished by reaction of the carbene complexes with either [AuCl(PPh3)] or [Ru(p-cym)Cl2]2 in the presence of KOH or LiHMDS as deprotonating agents. A number of Fe(ii)/Au(i) and Fe(ii)/Ru(ii) heterometallic complexes have been prepared in this way, some of them formally containing unique metalla-N-heterocyclic carbene ligands.
AB - A variety of half-sandwich iron(ii) complexes with diprotic acyclic diaminocarbene ligands (pADCs) have been obtained by reaction of the cationic complexes [Fe(Cp)(CO)2(CNR)]+ and [Fe(Cp)(CO)(CNR)2]+ with methylamine, and their acid-base behaviour was studied, revealing an easy reversible deprotonation reaction of both N-H moieties of the carbene ligands. The deprotonation process is frequently followed by a nucleophilic attack of the nitrogen atom on a vicinal carbonyl or isocyanide ligand, affording the corresponding metallacycles. Metalation of one or two N-H groups of the pADC ligands can be accomplished by reaction of the carbene complexes with either [AuCl(PPh3)] or [Ru(p-cym)Cl2]2 in the presence of KOH or LiHMDS as deprotonating agents. A number of Fe(ii)/Au(i) and Fe(ii)/Ru(ii) heterometallic complexes have been prepared in this way, some of them formally containing unique metalla-N-heterocyclic carbene ligands.
UR - http://www.scopus.com/inward/record.url?scp=85027106849&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1039/c7dt02049j
U2 - 10.1039/c7dt02049j
DO - 10.1039/c7dt02049j
M3 - Article
AN - SCOPUS:85027106849
VL - 46
SP - 10387
EP - 10398
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 31
ER -