129390-30-3Relevant academic research and scientific papers
Reaction of Tin Porphyrins with Vicinal Diols
Du, Guodong,Ellern, Arkady,Woo, L. Keith
, p. 2379 - 2386 (2008/10/09)
Reactions of tin porphyrins with vicinal diols were investigated. Treatment of (TTP)Sn(C≡CPh)2 or (TTP)Sn(NHtolyl)2 with pinacol and 2,3-diphenylbutane-2,3-diol afforded diolato complexes (TTP)Sn[OC(Me)2C(Me)2O]
Facile Syntheses of Titanium(II), Tin(II), and Vanadium(II) Porphyrin Complexes through Homogeneous Reduction. Reactivity of trans-(TTP)TiL2 (L = THF, t-BuNC)
Wang, Xiaotai,Gray, Steve D.,Chen, Jinyuan,Woo, L. Keith
, p. 5 - 9 (2008/10/08)
Facile syntheses of the meso-tetra-p-tolylporphyrin (TTP) complexes trans-(TTP)Ti(THF)2 (1), (TTP)Sn (2), and trans-(TTP)V(THF)2 (3) are achieved through homogeneous reduction of high-valent precursors using NaBEt3H. The composition of the new compound trans-(TTP)Ti(THF)2 was determined by spectroscopic and chemical characterization. Ligand displacement reactions of trans-(TTP)Ti(THF)2 with t-BuNC produced a new Ti(II) complex, trans-(TTP)Ti(t-BuNC)2. The ligand-binding preference of (TTP)TiIILn (n = 1, 2) is picoline ～pyridine > t-BuNC > PhC≡CPh > EtC≡CEt > THF.
Syntheses and Characterizations of Alkyl- And Amidotin Porphyrin Complexes: Molecular Structure of trans-Bis(phenylacetylido)(meso-tetra-p-tolylporphyrinato)tin(IV)
Chen, Jinyuan,Woo, L. Keith
, p. 3269 - 3275 (2008/10/08)
Treatment of (TTP)SnCl2 (TTP = mesotetra-p-tolylporphyrinato dianion) with an excess of lithium amides (LiNHPh, LiNPh2, o-C6H4(NHLi)2) affords the metathesis products (TTP)Sn(NHPh)2 (1), (TTP)Sn(NPh2)2 (2), and (TTP)Sn(o-C6H4(NH)2) (3). Ligand exchanges of 1 with p-toluidine and 2,3,5,6-tetrafluoroaniline afford the complexes (TTP)Sn(P-NHC6H4Me)2 (4) and (TTP)Sn(NHC6F4H)2 (5), respectively. Treatment of (TTP)SnCl2 with the bulky lithium (2,4,6-tri-terT-butylphenyl)amide or with PhNLiNLiPh does not form the corresponding amido or azobenzene complexes but produces the reduced product (TTP)Sn. In addition, the reaction of (TTP)-Sn(NHPh)2 with PhHN-NHPh results in the production of (TTP)Sn, azobenzene, and aniline. The diethyl complex (TTP)SnEt2 (6) can be prepared via the reaction of (TTP)SnCl2 with 1 equiv of ZnEt2. The dineopentyl complex (TTP)Sn(CH2CMe3)2 (7) can be detected in the reaction of (TTP)SnCl2 with neopentyllithium. The methyl derivatives cis-(TTP)SnMe2 (8) and (TTP)SnMeBr (9) can be obtained by the treatment of (TTP)Li2(THF)2 with 1 equiv of Me2SnBr2 at low temperature in toluene and CH2Cl2, respectively. Treatment of (TTP)SnCl2 with an excess of alkynyllithium salts (LiC≡CPh, LiC≡CSiMe3) affords the metathesis products (TTP)Sn(C≡CPh)2 (10) and (TTP)Sn(C≡CSiMe3)2 (11). Complexes 10 and 11 are inert at ambient temperature and are not photosensitive. Complex 10 reacts stepwise with excess MeOH cleanly to convert to (TTP)Sn(C≡CPh)(OMe) (12) and then to (TTP)Sn(OMe)2 (13) with increasing reaction time. The lability of the axial ligands in these tin porphyrin complexes correlates inversely with the basicity of the axial group. The crystal structure of 10 (monoclinic, P21/c, a = 10.9424(2) A, b = 14.5565(5) A, c = 16.4968(6) A, a = 90°, β = 100.7930(10)°, γ = 90°, R1, = 3.53%, and wR2 = 8.90%) was determined from X-ray diffraction data.
Synthesis, characterization, and reactivity of sulfido- and selenidomolybdenum(IV) porphyrin complexes. X-ray structure of sulfido(5,10,15,20-tetratolylporphyrinato)molybdenum(IV)
Berreau, Lisa M.,Young Jr., Victor G.,Woo, L. Keith
, p. 3485 - 3490 (2008/10/08)
Treatment of (TTP)Mo(PhC≡CPh) (TTP = meso-tetra-p-tolylporphyrinato) with S8 or Cp2TiS5 in toluene results in the formation of (TTP)Mo=S. The sulfide complex may also be prepared from the treatment of (TTP)MoCl2 with Li2S in THF. Similarly, a terminal selenide complex may be prepared from treatment of (TTP)MoCl2 with Na2Se. The structure of (TTP)Mo=S has been determined by single-crystal X-ray diffraction analysis (triclinic, P1, a = 12.735(2) ?, b = 13.521(2) ?, c = 13.920(2) ?, α = 74.76(1)°, β = 78.95(1)°, γ = 80.85(1)°, V = 2254.7(5) ?3, Z = 2, R = 3.1%, Rw = 4.2%). Complete sulfur atom transfer occurs between (TTP)Mo(PhC≡CPh) and (TTP)Sn=S to give (TTP)Mo=S, (TTP)SnII, and PhC≡CPh. The net result is a formal two-electron redox process that occurs irreversibly between Sn(IV) and Mo(II). Correspondingly, no reaction is observed between (TTP)Mo=S and (TTP)SnII in the presence of excess PhC≡CPh. The analogous treatment of (TTP)Mo(PhC≡CPh) with (TTP)Sn=Se results in the reversible exchange of a selenium ligand to form (TTP)Mo=Se, (TTP)SnII, and PhC≡CPh. When treated with excess PPh3, the sulfido or selenido complex is reduced to (TTP)Mo(PPh3)2 with formation of either Ph3P=S or Ph3P=Se. However, when (TTP)Mo=S or (TTP)Mo=Se is reduced with PPh3 in the presence of PhC≡CPh, (TTP)Mo(PhC≡CPh) is formed. The alkyne ligand of (TTP)Mo(PhC≡CPh) may be displaced by 4-picoline to give trans-(TTP)Mo(4-picoline)2. Ligand preference for the porphyrin Mo(II) center is thus PPh3 PhC≡CPh 4-picoline.
Tin(II) porphyrins: Synthesis and spectroscopic properties of a series of divalent tin porphyrins. X-ray crystal structure of (2,3,7,8,12,13,17,18-octaethylporphinato)tin(II)
Barbe,Ratti,Richard,Lecomte,Gerardin,Guilard
, p. 4126 - 4130 (2008/10/08)
A series of tin(II) porphyrins (P)Sn, where P is the dianion of octaethylporphyrin (OEP), tetraphenylporphyrin (TPP), tetra-p-tolylporphyrin (TpTP), tetra-m-tolylporphyrin (TmTP), and tetramesitylporphyrin (TMP), were synthesized and characterized by IR, UV-visible, 1H NMR, and 119Sn M?ssbauer spectroscopy. The crystal structure of (OEP)Sn(II), monomeric in the solid state (orthorhombic, Pnma; a = 9.489 (1), b = 15.171 (2), c = 22.373 (2) ?; Z = 4; R(F) = 0.031, RW(F) = 0.036), shows that the central metal lies 1.018 ? from the mean nitrogen plane. Comparison of M?ssbauer and X-ray data of compounds of this type with those of (P)SnFe(CO)4 derivatives shows a formal +II oxidation state for the porphyrin metal.
