Synthesis and Structure of Fe(TIM)(CNBPh₃)₂:  TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene. Conversion of BPh₄^- into CNBPh₃^-

Abstract

Fe(TIM)(CNBPh3)2 (TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) was isolated from the reaction of a solution of FeCl2 in methanol, TIM, and acetic acid with NaCN and then NaBPh4. The CNBPh3 - ligand is generated from an unexpected transformation of BPh4 -.

Carbonyl(η5-cyclopentadienyl)(isocyanotriphenylborato-κC)(triphenylphosphine-κP)iron(II)

“…1). Only three crystal structures have been reported to date for iron-isocyanotriphenylborate complexes, namely [Fe(Me)-(CO) 2 (PMe 3 ) 2 (CNBPh 3 )] (Ginderow, 1980), [Fe(TIM)-(CNBPh 3 ) 2 ] (TIM is 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene; Amrhein et al, 1996) and trans-[FeH(CNBPh 3 )(dppe) 2 ] (dppe is diphenylphosphinoethane; Almeida et al, 1999).…”

“…The Fe-CN distance [1.866 (3) Å ] of the Fe1 molecule in (I) is the shortest among the reported structures; this distance is 1.910 (3) Å in [Fe(Me)(CO) 2 (PMe 3 ) 2 (CNBPh 3 )] (Ginderow, 1980), 1.904 (3) Å in [Fe(TIM)(CNBPh 3 ) 2 ] (Amrhein et al, 1996) and 1.914 (3) Å in trans-[FeH(CNBPh 3 )(dppe) 2 ] (Almeida et al, 1999). The Fe-C-N-B geometric parameters of the Fe1 and Fe2 molecules in (I) [N-B = 1.584 (4) and 1.587 (4) Å , Fe-C-N = 173.9 (3) and 174.6 (3) , and C-N-B = 173.8 (3) and 177.0 (3) ] are similar to those in the previously reported complexes.…”

Synthesis and properties of iron-group hydrido-cyano complexes trans-[MH(CN)(L)2], M = Fe, Ru or Os, L = diphosphine, and their hydrogen, trifluoroboron and triphenylboron isocyanide derivatives of the type trans-[MH(CNH)(L)2]O3SCF3, trans-[MH(CNBX3)(L)2], X = F or Ph, and trans-[M(H2)(CNBF3)(dppp)2]BF4 [dppp = Ph2P(CH2)3PPh2]

“…Amrhein et al (TIM = 2,3,9,10-tetramethyl-1,4,8,11tetraazacyclotetradeca-1,3,8,10-tetraene). 15 Certainly the well known affinity of the CN ligand for BPh 3 34 helps to drive the reaction.…”

“…By using KC15 N or K13 CN the corresponding derivatives trans-[RuH(C 15 N)(dppp) 2 ] 1Ru3-n and trans-[RuH( 13 CN)-(dppp) 2 ] 1Ru3-c have also been prepared. The IR spectra of the complexes in Nujol mulls show a ν(CN) absorption at 2039 (1Ru3-n) and 2024 (1Ru3-c) compared to 2069 cm Ϫ1 for 1Ru3 (Table…”

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part I); Synthesis and Characterization of Cr(III)-Benzoato and Chlorobenzoato Macrocyclic Complexes

“…[7][8][9] In recent years there have been many investigations of the synthesis, structures, and properties of various types of Nfunctionalized tetraaza macrocyclic ligands and their transition metal complexes. [10][11][12] In particular, the reactivity of nickel-or cobalt-macrocyclic complexes toward Lewis bases like oxalate has been explored in detail. [13][14][15][16][17] Eriksen and cowokers recently attempted to characterize the complex formation between carboxylic acids/carboxylates in particular acetic acid/acetate and macrocyclic chromium complexes exemplified by cis complexes of rac- 5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane (L m = [14]decane) and cyclam.…”