Organobismuth(III) and Organobismuth(V) Complexes Containing Pyridyl and Amino Functional Groups. Syntheses and Characterizations of Bi^IIIAr₃ (Ar = p-C₆H₄(NMe₂), p-C₆H₄CH₂(NPrⁱ₂), p-C₆H₄[CH₂N(2-Py)₂]), Bi^VAr₃L₂, [Bi^VAr₃Cl]₂O, [Bi^VAr₄][PF₆

Abstract

The synthesis of tertiary bismuth(III) complexes containing amino or pyridyl functional groups has been investigated. An improved synthesis for Bi[p-C6H4(NMe2)]3 (1) has been achieved. Two new complexes, Bi[p-C6H4CH2(NPri 2)]3 (2) and Bi[p-C6H4CH2N(2-Py)2]3 (3), have been obtained. The bismuth(V) derivatives of compounds 1 and 3 have been synthesized via chlorine oxidation of 1 and 3 and the subsequent substitution reactions. Compounds Bi[p-C6H4(NMe2)]3(O2CCF3)2 (5) and Bi{p-C6H4[CH2N(2-Py2)]}3(O2CCH3)2 (7) were obtained from the reactions of the corresponding dichloride complexes, BiAr3Cl2, with the appropriate silver salt. NMR spectroscopic studies established that in solution, compound 5 is fluxional while compound 7 is rigid. A dinuclear complex Bi2[p-C6H4(NMe2)]6Cl2(O) (6) was isolated as the major product when the dichloride complex Bi[p-C6H4(NMe2)]3Cl2 was reacted with NaOH in nondistilled reagent grade dichloromethane. A quaternary bismuth(V) complex, Bi[p-C6H4(NMe2)]4[PF6] (8), was obtained in good yield when Bi[p-C6H4(NMe2)]3Cl2 was reacted with TlPF6 in a 1:2 ratio. A closely related quaternary bismuth(V) complex {Bi[p-C6H4(NMe2)]4}2[Ag2Cl4] (9), which contains an unusual three-coordinate dinuclear anion Ag2Cl4 2-, was obtained as a trace product from the reactions of Bi[p-C6H4(NMe2)]3Cl2 with silver salts. The crystal structures of compounds 1 and 5−9 were determined by single-crystal X-ray diffraction analyses.

Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study

“…In order to develop a better understanding with regard to the effects of substituents, (C 6 H 4 -OMe-4) 3 Bi ( 3 ) [50–51] was prepared starting from BiCl 3 and the corresponding organolithium reagent following a general method as reported by Wang et al [52]. Compound 3 was obtained as colorless block-shaped crystals in yields of 83%.…”

Molekülverbindungen mit Mo‐O‐Bi‐Einheiten

“…Die Phenylringe besetzen die äquatorialen Koordinationsstellen in einer für Ph 3 BiX 2 ‐Strukturen üblichen Weise 11a. Die Mo‐O‐Bi‐Einheiten sind gewinkelt (Mo1‐O1‐Bi 139.5(3)°, Mo2‐O4‐Bi 152.8(3)°), und die Bi‐O‐Abstände sind mit 2.198(6) (Bi‐O1) und 2.204(6) Å (Bi‐O4) etwas größer als diejenigen in den bekannten μ‐Oxo‐verbrückten zweikernigen Organobismut( V )‐Verbindungen des Typs [(Ar 3 BiY) 2 O] (2.02–2.12 Å; Y=ClO 4 − , CF 3 SO 3 − , Ar=Ph; Y=Cl − , Ar=4‐(Me 2 N)C 6 H 4 ) 11b–d. Dies mag daraus resultieren, dass die beiden Oxoliganden in 1 trans zueinander angeordnet sind und als starke π‐Acceptoren um dieselben Metallorbitale konkurrieren, wodurch sie ihre Bindungen gegenseitig schwächen.…”

Selective Photooxidation of Sulfides Catalyzed by Bis‐cyclometalated IrIII Photosensitizers Bearing 2,2′‐Dipyridylamine‐Based Ligands

“…This procedure was adapted and optimized from those reported in the literature. [20][21][22][23][24] The Ir III complexes [1]Cl- [4]Cl of general formula [Ir(C _ N) 2 (N _ N)]Cl (C _ N = 2-phenylpyridinate (ppy À ), N _ N = L1-L4) were synthesized according to the classical procedure, [25] which involvest wo steps:preparation of the well-known chlorido-bridged dimer [{Ir(m-Cl)(C _ N) 2 } 2 ], followed by reactionw ith the correspondingN _ Nl igand in CH 2 Cl 2 /MeOHa t5 0 8C (Scheme 2). The desired compounds were obtained in good yields as the chloride salts of the Ir III cationic complexes in the form of racemic mixtures (L and D enantiomers).T hey are airand moisture-stable yellow solids,s oluble in common organic solvents.…”