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1.
Prithwiraj Byabartta 《Transition Metal Chemistry》2007,32(6):716-726
[Au(C6F5)(tht)], which on reaction with P, O, S-coordinating phosphines in CH2Cl2 medium leads to [Au(C6F5)(X)] [X = PPh3 H, (1a), oMe, (1b), pMe, (1c), mMe, (1d), AsPh3
(2), OPPh3
(3), SPPh3
(4), dppm, dppe, dppa = diphenylphosphino-methane,-ethane,-ammine(5, 6, 7), TPA = 135-tetraaza-7-phosphino adamentane(8), Py4H (9a), 4Bu (9b), 4Ac (9c), tht = tetrahydrothiophen, C6F5 is the pentafluorophenyl ring]. The maximum molecular peak of the corresponding molecule is observed in the ESI mass spectrum.
I.r. spectra of the complexes show –C = C– and C6F5 stretching near at 1610 and 1510, 955, 800 cm−1. The 1H-n.m.r. spectra as well as 31P- (1H)n.m.r. suggest solution stereochemistry, proton movement, phosphorus proton interaction. 13C-n.m.r. spectrum reflect the carbon skeleton in the molecule. In the 1H–1H COSY spectrum of the present complexes and contour peaks in the 1H–13C-HMQC spectrum, assign the solution structure and stereoretentive conformation in each step. 相似文献
2.
3.
BYABARTTA Prithwiraj 《中国化学》2008,26(8):1515-1518
Reaction of [Au(DAPTA)(Cl)] with RaaiR’ in CH2Cl2 medium following ligand addition leads to [Au(DAPTA)(RaaiR’)](Cl) [DAPTA=diacetyl-1,3,5-triaza-7-phosphaadamantane, RaaiR’=p-R-C6H4-N=N- C3H2-NN-1-R’, (1—3), abbreviated as N,N’-chelator, where N(imidazole) and N(azo) represent N and N’, respectively; R=H (a), Me (b), Cl (c) and R’=Me (1), CH2CH3 (2), CH2Ph (3)]. The 1H NMR spectral measurements in D2O suggest methylene, CH2, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C NMR spectrum in D2O suggest the molecular skeleton. The 1H-1H COSY spectrum in D2O as well as contour peaks in the 1H-13C HMQC spectrum in D2O assign the solution structure. 相似文献
4.
P. Byabartta 《Russian Journal of Coordination Chemistry》2009,35(8):582-587
The hetero-tris-chelates of the formula [Ru(Phen)(RAaiR′)2](ClO4)2 (Phen = 1,10-phenanthroline, RAaiR′ = 1-alkyl-2-(arylazo)imidazole, p-R-C6H4-N=N-C3H2-NN-1-R′, where R = H (a), Me (b), Cl (c) and R′ = Me (II), Et (III), CH2Ph (IV)) have been isolated from the reaction of ctc-[RuCl2(RAaiR′)2] with AgNO3 + Phen or [Ag(Phen)2](ClO4) in acetone at 40°C in dark followed by the addition of NaClO4 (aq). The stereo-chemistry of the complexes have been supported by 1H NMR data. Considering the arylazoimidazole and phenanthroline moietie there are twenty different carbon atoms in the molecule
which gives a total of twenty different peaks in the 13C NMR spectrum of complex Ia. Cyclic voltammograms show Ru(III)/Ru(II) couple at 1.3–1.4 V vs SCE along with three successive ligand reductions.
The article is published in the original. 相似文献
5.
P. Byabartta 《Russian Journal of Coordination Chemistry》2009,35(9):687-691
Silver-assisted aquation of blue cis-trans-cis-RuCl2(RAaiR’)2 (I) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH2)2(RAaiR’)2](ClO4)2 (II), where RAaiR’ = p-R-C6H4-N=N-C3H2-NN, abbreviated as N,N′ chelator (N(imidazole) and N(azo) represent N and N′, respectively); R = H (a), p-Me (b), p-Cl(c); R′ = Me (III), Et (IV), Bz (V), that reacted with NCS− in warm EtOH resulting in red-violet dithiocyanato complexes of the type [Ru(NCS)2(RAaiR)2] (IIIa–Vn). These complexes were studied by elemental analysis, UV-Vis, IR, and 1H NMR spectroscopy and cyclic voltammetry. The solution structure and stereoretentive transformation in each step have been
established from 1H NMR results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display
one metal-centered oxidation and successive ligand-based reductions. Linkage isomerisation was studied by changing the solvent
and then by UV-Vis spectral analysis. 相似文献
6.
P. Byabartta 《Russian Journal of Coordination Chemistry》2009,35(7):482-485
Aromatic ring amination reactions in the ruthenium complex of 1-methyl-2-(phenylazo)imidazole is described. The substitutionally
inert cationic brown complex [Ru(HAaiMe)3](ClO4)2(I) reacts smoothly with aromatic amines neat and in the presence of air produce cationic and intense blue complexes [Ru(ArNH-AaiMe)3](ClO4)2 (II) (ArNH-AaiMe = 1-methyl-2-[(4-(arylamino)phenyl)azo] imidazole, Ar = C6H5 (IIa), p-C6H4Me (IIb)). These were purified on a preparative TLC plate (large plates of thin layer chromatography). The results are compared
with those of the starting complex, [Ru(HAaiMe)3](ClO4)2 (I). The transformation I → II involves aromatic ring amination at the para carbon (with respect to the diazo function) of the pendant phenyl rings of all three coordinated azoimine ligands in I. The ruthenium complex II is characterized by intense blue solution color. The lowest energy transitions in these complexes appear near 600 nm, which
have been attributed to intraligand charge-transfer transitions. IR spectra of the complexes show -C=N- and -N=N- stretching
at 1590 and 1370 cm−1 which is red shifted by 40 and 90 cm−1 from the free ligand value and supports Ru-azo nitrogen π bonding interection. The 1H NMR spectral measurements suggest methyl and aromatic ring protons. Considering three arylazoimidazole moities there are
forty eight different carbon atoms in the molecule which gives a total of that different peaks in the 13C (1H) NMR spectrum. In the 1H-1H COSY spectrum of the present complex, absence of any off-diagonal peaks extending from δ = 14.12 and 9.55 ppm confirms their
assignment of no proton on N(1) and N(3), respectively. Contour peaks in the 1H-13C HMQC spectrum in the present complex assign them hydrogen carbon atoms relationship, respectively. The electrons are believed
to be added successively to the three azo functions.
The article is published in the original. 相似文献
7.
Prithwiraj Byabartta 《Transition Metal Chemistry》2005,30(8):978-986
The reaction of ctc-[Ru(RaaiR′)2Cl2] (3a–3i) [RaaiR′=1-alkyl-2-(arylazo)imidazole, p-R—C6H4—N=N— C3H2NN(1)—R′, R=H, OMe, NO2, R′=Me, Et, Bz] with KS2COR′′ (R′′=Me, Et, Pr, Bu or CH2Ph) in boiling dimethylformamide afforded [RuII{o-S—C6H4(p-R-)—N=N—C3H2NN(1)—R′}2] (4a–4i), where the ortho-carbon atom of the pendant phenyl ring of both ligands has been selectively and directedly thiolated. The newly formed tridentate
thiolate ligands are bound in a meridional fashion. The solution electronic spectra exhibit a strong MLCT band near 700 nm
and near 550 nm, respectively in DCM. The molecular geometry of the complexes in solution has been determined by H n.m.r.
spectroscopy. Cyclic voltammograms show a Ru(II)/Ru(III) couple near 0.4 V and an irreversible oxidation response near 1.0
V due to oxidation of the coordinated thiol group, along with two successive reversible ligand reductions in the range −0.80–0.87
V (one electron), −1.38–1.42 V (one electron). Coulometric oxidation of the complexes at 0.6 V versus SCE in CH2Cl2 produced an unstable Ru(III) congener. When R=Me the presence of trivalent ruthenium was proved by a rhombic e.p.r. spectrum
having g1=2.349, g2=2.310. 相似文献
8.
Prithwiraj Byabartta 《Transition Metal Chemistry》2007,32(8):1007-1011
Reaction of [Au(C6F5)(tht)2Cl](OTf) with RaaiR′ in CH2Cl2 medium leads to [Au(C6F5)(RaaiR′)Cl](OTf) [RaaiR′ = p-R–C6H4–N=N–C3H2–NN-1-R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH2CH3
(2), CH2Ph (3), tht is tetrahydrothiophen]. The maximum molecular peak of [Au(C6F5)(MeaaiMe)Cl] is observed at m/z 599.51 (100 %) in the FAB mass spectrum. Ir spectra of the complexes show –C=N– and –N=N– stretching near at 1590 and 1370 cm−1 and near at 1510, 955, 800 cm−1 due to the presence of pentafluorophenyl ring. The 1H-NMR spectral measurements suggest methylene, –CH2–, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph shows AB type quartets. 13C-NMR spectrum of complexes confirm the molecular skeleton. In the 1H-1H-COSY spectrum as well as contour peaks in the 1H-13C HMQC spectrum for the present complexes, assign the solution structure and stereoretentive conformation. The electrochemistry
gives the ligand reduction peaks. 相似文献
9.
Prithwiraj Byabartta 《Transition Metal Chemistry》2007,32(3):314-324
Silver assisted de-bromination gives [Au2(dppm/dppe/dppa) (OTf)2], which on reaction with 4,4′-bpy and gold(I) phosphines in CH2Cl2 medium, by the self assembly technique, leads to [(PPh3)Au(4,4′-bpy)Au(PPh3)], (1a–1d,2), [{Au2(dppm/dppe/dppa)}{(4,4-bpy)Au(PPh3)}2](NO3)4, (3), [{Au4(dppm/dppe/dppa)2(4,4-bpy)2}](OTf)4,
(4), [{(PPh3)AuI(4,4′-bpy)}2AuIII(C6F5/Mes)](NO3)3, (5) [dppm/dppe/dppa =diphenyl phosphino-methane(a), –ethane(b), ammine(c), C6F5/Mes pentafluorophenyl/mesitylene]. The maximum molecular peak of the corresponding molecule is observed in the ESI mass spectrum.
Ir spectra of the complexes show –C=C–, –C=N–, as well as phosphine, mesitylene and pentafluorophenyl stretching. The 1H-NMR spectra as well as 31P(1H)-NMR suggest solution stereochemistry, proton movement and phosphorus proton interaction. Considering all the moities there
are a lot of carbon atoms in the molecule reflected by the 13C(H)-NMR spectrum. In the 1H–1H COSY spectrum of the present complexes and contour peaks in the 1H–13C-HMQC spectrum, assign the solution structure and stereoretentive transformation in each step. 相似文献
10.
Prithwiraj Byabartta 《Transition Metal Chemistry》2007,32(3):304-313
Reaction of [Au(PPh3)2(tht)2](OSO2CF3)3 with RaaiR′ in CH2Cl2 medium following ligand addition leads to [Au(PPh3)2(RaaiR′)](OTf)3 [RaaiR′ = p-R–C6H4–N=N–C3H2–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH2CH3
(2), CH2Ph (3), PPh3 is triphenylphosphine, OSO2CF3 is the triflate anion, tht is tetrahydrothiophen]. The maximum molecular peak of the corresponding molecule is observed in
the ESI mass spectrum. The 1H-nmr spectral measurements suggest methylene, –CH2–, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C-nmr spectrum suggests the molecular skeleton. In the 1H–1H COSY spectrum as well as contour peaks in the 1H–13C heteronuclear multiple-quantum coherence (HMQC) spectrum assign the solution structure. Electrochemistry assign ligand reduction
part rather than metal oxidation. 相似文献