The hybrid dibismuthines O(CH2CH2BiPh2)2 and MeN(CH2-2-C6H4BiPh2)2 react with [M(CO)5(thf)] (M = Cr or W) to form [{M(CO)5}2{O(CH2CH2BiPh2)2}] and [{Cr(CO)5}2{MeN(CH2-2-C6H4BiPh2)2}] containing bridging bidentate (Bi2) coordination. The unsymmetrical tertiary bismuthine complexes [M(CO)5{BiPh2(o-C6H4OMe)}] are also described. Depending upon the molar ratio, the hybrid distibines O(CH2CH2SbMe2)2 and MeN(CH2-2-C6H4SbMe2)2 react with [M(CO)5(thf)] to give the pentacarbonyl complexes [{M(CO)5}2{O(CH2CH2SbMe2)2}] and [{Cr(CO)5}2{MeN(CH2-2-C6H4SbMe2)2}] or tetracarbonyls cis-[M(CO)4{O(CH2CH2SbMe2)2}] and cis-[M(CO)4{MeN(CH2-2-C6H4SbMe2)2}]. The latter can also be obtained from [Cr(CO)4(nbd)] or [W(CO)4(pip)2], and contain chelating bidentates (Sb2-coordinated) as determined crystallographically. S(CH2-2-C6H4SbMe2)2 coordinates as a tridentate (SSb2) in fac-[M(CO)3{S(CH2-2-C6H4SbMe2)2}] (M = Cr or Mo) and fac-[Mn(CO)3{S(CH2-2-C6H4SbMe2)2}][CF3SO3]. Fac-[Mn(CO)3{MeN(CH2-2-C6H4SbMe2)2}][CF3SO3] contains NSb2-coordinated ligand in the solid state, but in solution a second species, Sb2-coordinated and with a κ1-CF3SO3 replacing the coordinated amine is also evident. X-ray crystal structures were also determined for fac-[Cr(CO)3{S(CH2-2-C6H4SbMe2)2}], fac-[Mn(CO)3{S(CH2-2-C6H4SbMe2)2}][CF3SO3] and fac-[Mn(CO)3{MeN(CH2-2-C6H4SbMe2)2}] [CF3SO3]. Hypervalent N⋯Sb interactions are present in cis-[M(CO)4{MeN(CH2-2-C6H4SbMe2)2}] (M = Mo or W), but absent for M = Cr.

Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls.

New stable divalent heterocyclic species [SnL1; 1, SnL2; 2] using ONNO and SNNS tetradentate Schiff bases; N,N′-bis(salicylidene)-1,2-bis(o-aminophenoxy)ethane (H2L1) and N,N′-bis(2-aminothiophenol)-1,4-bis(2-carboxaldehydephenoxy)butane (H2L2) were obtained in good yields by alcolysis of the M-N bonds of the divalent precursor Sn[N(SiMe3)2]2 by diols. They have been isolated as solids at ambient temperature and are monomeric. FT-IR, 1H and 119Sn-NMR spectra are suggestive of N … M intramolecular coordination. Then the synthesis and characterization of the new stable mono and cis-disubstituted Sn(II) chromium and tungsten carbonyl complexes [L1Sn]M(CO)5 (M= Cr, 3; W, 4); [L2Sn]M(CO)5 (M= Cr, 5; W, 6); cis-[L1Sn]2M(CO)4 (M= Cr, 7; W, 8) and cis-[L2Sn]2M(CO)4 (M= Cr, 9; W, 10) are described. Pentacarbonyl complexes (3–6) were obtained in high yields by treatment of the M(CO)5THF (M= Cr, W) intermediates with the divalent species [SnL1; 1, SnL2; 2] and tetracarbonyl complexes (7–10) were synthesized by the p...

Synthesis and Characterization of Stable Hetereocyclic (Schiff Base) Divalent Tin Species and Photogeneration of Their Transition Metal Carbonyl Complexes

The coordination behavior of different pnictogenylboranes towards group 6 metal Lewis acids is investigated. The resulting complexes with phosphanylboranes [(CO)4M(PH2BH2 ⋅ NMe3)2] (M=Cr, Mo, W; 1–3), arsanylboranes ([(CO)4M(AsH2BH2 ⋅ NMe3)2] (M=Cr, Mo, W; 4–6) and tBu-substituted phosphanylboranes [(CO)4M(tBuPHBH2 ⋅ NMe3)2] (M=Cr, W; 7–8) are fully characterized by multinuclear NMR spectroscopy, single crystal X-ray diffraction and IR spectroscopy. The systematic nature of the approach of the synthesis and the high purity of the compounds enable a comparative investigation of the coordination behavior of pnictogenylboranes. The influences of the metal center, the pnictogen atom and the substituent at the pnictogen atom on the coordination behavior of pnictogenylboranes are compared. 

Coordination chemistry of pnictogenylboranes towards group 6 transition metal Lewis acids

New complexes cis-[M(CO)4-DABRd] (M = Cr(I), Mo(II) and fac-[M(CO)3-SAT] (M = Cr(III), Mo(IV)) have been synthesized by the photochemical reactions of cis-[(η4-NBD)M(CO)4] (NBD is norbornadiene; M=Cr, Mo) with 5-(4-dimethylaminobenzylidene) rhodanine (DABRd) and salicylidene-3-amino-1,2,4-triazole (SAT) ligands and characterized by elemental analysis, FT-IR and 1H NMR spectroscopy, and mass spectrometry. The spectroscopic studies show that the DABRd ligand acts as a bidentate ligand coordinating via both NH-(S)C=S sulfur donor atoms in I and II and SAT ligand behaves as a tridentate ligand coordinating via its all imine nitrogen-C=N-donor atoms in III and IV to the metal center.

A. Ercag

Papers

Photochemical reactions of cis-[(η4-NBD)M(CO)4] (NBD = norbornadiene; M = Cr, Mo) olefin complex with ligand, containing S and N donor atoms