Structural and Spectroscopic Studies on the Dimeric Complexes of Tris(2-methylphenyl)phosphine With Copper(I) Halides

1994 ◽  
Vol 47 (1) ◽  
pp. 25 ◽  
Author(s):  
GA Bowmaker ◽  
JV Hanna ◽  
RD Hart ◽  
PC Healy ◽  
AH White
Keyword(s):  
Solid State ◽  
Far Infrared ◽  
Spectroscopic Studies ◽  
Mixed Ligand ◽  
Acetonitrile Solution ◽  
Normal Coordinate ◽  
Dimeric Complexes ◽  
Copper Coordination ◽  
Binuclear Species ◽  
Far Infrared Spectra

1:1 adducts of the copper(I) halides, CuX (X = Cl, Br, I), with the sterically hindered ligand tris (2-methylphenyl) phospine [P(o- tol )3] have been synthesized as crystalline dihalo -bridged centrosymmetric binuclear species; six compounds have been characterized by solid-state CP-MAS n.m.r. and far-infrared spectroscopy and by room-temperature single-crystal X-ray structure determination. For X = Cl , the dimeric complex. [P(o- tol )3CuCl]2, with three-coordinate copper atoms has been obtained from acetonitrile solution. Similar dimeric complexes for X = Br and I were obtained from toluene solution, the iodide adduct incorporating cocrystallized toluene. The X = Br and I complexes crystallized from acetonitrile solution yield mixed- ligand four-coordinate copper(I) dimers, [( MeCN )P(o- tol )3CuX]2, the iodide as a 2MeCN solvate. An additional crystalline phase incorporating crystallographically independent molecules of both the three-coordinate dimer and the four-coordinate mixed- ligand dimer has also been characterized for X = Br. Solid-state 31P CP-MAS n.m.r. spectra of the complexes at B = 7.05 T show well resolved asymmetric quartets with a ∆v3/∆v1 of 1.4 for the PcuX2 complexes and 1.1-1.2 for the PcuX2N complexes; these results reflect the geometric and bonding changes in the copper coordination sphere. Far-infrared spectra of the complexes show two strong halogen-sensitive bands, with a wavenumber separation of 30-40 cm-1, which have been assigned to copper-halogen stretching modes v( CuX ), this assignment being supported by a normal coordinate analysis on the Cu2X2 core.

scholarly journals Far infrared spectra of solid state aliphatic amino acids in different protonation states

2010 ◽  
Vol 132 (11) ◽  
pp. 115105 ◽  
Author(s):  
Aurélien Trivella ◽  
Thomas Gaillard ◽  
Roland H. Stote ◽  
Petra Hellwig
Keyword(s):  
Amino Acids ◽  
Solid State ◽  
Infrared Spectra ◽  
Far Infrared ◽  
Far Infrared Spectra

Isotopic Studies of the Metal–Ligand Bond. Part II. The Far Infrared Spectra of Some Binuclear and Polymeric Copper Carboxylate Derivatives; Variable Temperature and Isotopic Studies of the Copper–Ligand Vibrations

1973 ◽  
Vol 51 (4) ◽  
pp. 514-519 ◽  
Author(s):  
A. B. P. Lever ◽  
B. S. Ramaswamy
Keyword(s):  
Infrared Spectra ◽  
Variable Temperature ◽  
Copper Acetate ◽  
Far Infrared ◽  
Dimeric Complexes ◽  
Isotopic Studies ◽  
Stretching Vibration ◽  
Amine Adducts ◽  
Far Infrared Spectra ◽  
Ligand Bond

The far infrared spectra of 16 adducts of pyridine, quinoline, isoquinoline, urea, aniline, o- and p-toluidine with copper acetate, propionate, and butyrate, and of copper formate tetrahydrate were recorded at ambient temperature and at −196 °C. A range of derivatives were prepared containing isotopically pure 65Cu. The spectra of these derivatives were used to identify, unequivocally, the copper–oxygen stretching frequencies.Complexes believed to be polymeric (aniline and toluidine adducts) exhibit one copper–oxygen stretching vibration between 300 and 350 cm−1 A second band, lying between 350 and 400 cm−1 is not isotopically sensitive. The dimeric complexes exhibit one or two bands in the 300–400 cm−1 region, all of which are isotopically sensitive. Certain of the amine adducts exhibit an isotopically sensitive band near 240 cm−1 assignable to a Cu—N stretching mode.

Synthesis, Structures and Spectroscopic Properties of 1 : 1 Complexes of Gold(I) Halides with Trimesitylphosphine

2000 ◽  
Vol 53 (3) ◽  
pp. 175 ◽  
Author(s):  
Raymond C. Bott ◽  
Graham A. Bowmaker ◽  
Robbie W. Buckley ◽  
Peter C. Healy ◽  
M. C. Senake Perera
Keyword(s):  
Infrared Spectroscopy ◽  
Solid State ◽  
Far Infrared ◽  
Spectroscopic Properties ◽  
Far Infrared Spectroscopy ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Structure Determinations ◽  
Far Infrared Spectra

Monomeric two-coordinate gold(I) complexes, [Au(P(mes)3)X] (P(mes)3 = tris(2,4,6-trimethylphenyl)phosphine, X = Cl, Br and I), have been prepared and characterized by single-crystal X-ray structure determinations, far-infrared spectroscopy and solution and solid-state CPMAS 31 P n.m.r. spectroscopy. X-Ray structure determinations show that crystals obtained from solutions of [NBu4] [AuX2] and P(mes)3 in acetonitrile for X = Cl, Br and I and in dimethylformamide (dmf) for X = Br and I form an isomorphous series of complexes, crystallizing in space group P21/c with a ª 8, b ª 22, c ª 13 Å, b ª 98˚ (a form). Crystallization of the chloride from dimethylformamide yields the solvated complex [Au(P(mes)3)X]·(dmf) in space group P2/a with a 15.224(2), b 10.070(1), c 18.210(4) Å, b 100.42(2)˚. Electrochemical synthesis of the complexes for X = Cl and Br yield two new crystalline phases; the chloride in space group P21/c with a 10.249(2), b 8.189(2), c 31.844(3) Å, b 91.68(1)˚ (b form) and the bromide in space group Pbca with a 19.208(4), b 15.586(3), c 16.962(4) Å ( g form). The Au–P bond lengths increase in the order Cl < Br < I with distances c. 0.02–0.03 Å longer than average values for other [Au(PR3)X] complexes, reflecting steric congestion by the P(mes)3 ligand. For the unsolvated complexes, the Au–X distances are c. 0.02 Å shorter than average values. For the Cl/dmf solvate, both Au–P and Au–X bond lengths increase. For the a complexes, far-infrared spectra show n(Au 35,37 Cl) 336, 329 cm –1 , n(AuBr) 234 cm –1 and n(AuI) 195 cm –1 and solid-state 31 P CPMAS n.m.r. spectra yield broad peaks with d–3.9 (Cl), –0.6 (Br) and +6.0 I). For the Cl/dmf solvate, n(Au 35,37 Cl) are 334, 327 cm –1 and d is –4.4. Solution 31 P n.m.r. spectra in CDCl3 give sharp single peaks at d –5.0 (Cl), –1.4 (Br) and +5.5 (I) with the similarity of the values with those for the solid-state spectra consistent with similar conformational structures for the [Au(P(mes)3)X] molecules in the two states.

scholarly journals Nature of the coordination bond in metal complexes of substituted pyridine derivatives. IV. Skeletal vibration spectra and the substituent effect upon the coordination bond of the pyridine complex of zinc(II) ion

1969 ◽  
Vol 47 (24) ◽  
pp. 4589-4597 ◽  
Author(s):  
Patrick T. T. Wong ◽  
D. G. Brewer
Keyword(s):  
Previous Investigation ◽  
Copper Complexes ◽  
Far Infrared ◽  
Coordination Bond ◽  
Pyridine Derivatives ◽  
Normal Coordinate ◽  
Absorption Bands ◽  
Pyridine Complex ◽  
Far Infrared Spectra ◽  
Coordinate Treatment

Far infrared spectra of the complexes Zn(pyridine)2X2, where X = Cl or Br, have been investigated in the region 350–20 cm−1. Eight infrared-active skeletal modes of these complexes have been observed, and a tentative assignment of these absorption bands has been made. The previous investigation of the effect of substituents upon the coordination bond of the copper–pyridine complex has been extended to the zinc–pyridine complex in the present paper. It was found that the relative zinc–pyridine bond strength, affected by the substituents, is determined by both the relative σ-contribution and π-contribution to the bond, rather than mainly by the σ-contribution as in the system of copper complexes. The force constants associated with the zinc–pyridine coordination bond of a series of 4-substituted pyridine complexes have been calculated by a normal coordinate treatment described in previous papers in this series.

Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. V Bismuth(III) Halide/N,N′-Bidentate Ligand (1 : 2) Systems

1998 ◽  
Vol 51 (4) ◽  
pp. 331 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Frances M. M. Hannaway ◽  
Peter C. Junk ◽  
Aaron M. Lee ◽  
Brian W. Skelton ◽  
...  
Keyword(s):  
Single Crystal ◽  
Infrared Spectra ◽  
Room Temperature ◽  
Far Infrared ◽  
Spectroscopic Studies ◽  
Bidentate Ligand ◽  
X Ray ◽  
B 31 ◽  
Far Infrared Spectra

Syntheses and room-temperature single-crystal X-ray determinations are recorded for a number of adducts of BiX3/N,N′-bidentate 1 : 2 stoichiometry (N,N′-bidentate = 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen)). BiX3/bpy (1 : 2), X = Br, I, are isomorphous, monoclinic, P21/c, a ≈ 7·5, b ≈ 31, c ≈ 10·3 Å, β ≈ 113°, Z = 4; conventional R on |F| were 0·058, 0·055 for No 1744, 2068 independent ‘observed’ (I > 3σ(I)) reflections. BiCl3/phen (1 : 2) is monoclinic, P21/C, a 9·675(3), b 31·845(7), c 7·756(2) Å, β 109·94(2), Z = 4, R 0·071 for No 2537, while BiBr3/phen (1 : 2), also monoclinic, P21/c, has a 17·590(5), b 8·812(2), c 17·537(7) Å, β 117·58(3)°, Z = 4; R 0·083 for No 890. BiX3/phen (1 : 2).S, X/S = Br/MeCN, I/CH2Cl2, are isomorphous, orthorhombic, Pna21, a ≈ 20·7, b ≈ 14·2, c ≈ 8·9 Å, Z = 4, R 0·060, 0·046 for No 1553, 2423 respectively. All complexes are mononuclear with seven-coordinate (N2)2BiX3 bismuth environments. Bands in the far-infrared spectra due to the v(BiX) vibrations in [(phen)2BiCl3] and [(bpy)2BiX3] (X = Br, I) are assigned and discussed in relation to the structures of the complexes.

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