Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

Abstract

Reactions of copper(I) halides with 1,1,1‐tris(diphenylphosphanylmethyl)ethane (triphos) in 1:1 molar ratio afforded mononuclear complexes of the type [CuX(triphos)] which on further treatment with one equivalent of the potassium thiolate salt of a heterocyclic thione gave rise to the formation of mixed‐ligand complexes of the formula [Cu(κ3‐triphos)(κ1‐thiolate)]. The molecular structures of [Cu(κ3‐triphos)(κ1‐py2S)]·C2H5OH (1) and [Cu(κ3‐triphos)(κ1‐pymt)] (2) have been established by single‐crystal X‐ray diffraction. The complexes adopt a rigid distorted tetrahedral geometry with the phosphane ligand acting in a tridentate chelating mode. The complexes are strongly luminescent in solution and in the solid state. The spectroscopic and electronic properties of the new copper(I) complexes have been computed by electronic structure computational techniques (TD‐DFT calculations), that contribute to the assignments of electronic spectra. The high‐energy absorptions in the absorption spectra of complexes 1 and 2, ranging from 210 to 270 nm, are assigned to MLCT/LLCT transitions and the same also holds true for the low‐energy absorptions found in the range 280 to 300 nm. In the lowest triplet excited state, T1, involved in the emission in the 456–502 nm range, the spin density is delocalized over the entire nuclear framework.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

The preparation of multimetallic complexes using sterically bulky N-centred tripodal dialkyl phosphino ligands

“…This was further supported by the IR spectrum complex 6 which showed a strong absorption at 2008 cm À1 and a broad peak with shoulders at 1888 cm À1 characteristic of a cis-tetracarbonyl complex [35]. Reaction of 4 with W(CO) 6 under the same reaction conditions gave [W(CO) 4 {N-(CH 2 PCy 2 ) 3 -j 2 P}] (7) which displayed a similar pattern in its 31 P{ 1 H} spectrum, showing a higher frequency chemical shift to 3.2 ppm, with 183 W satellites ( 1 J = 217 Hz), and a lower frequency resonance at À16.9 ppm accounting for the free phosphorus arm. The IR spectrum of this complex also indicated a tetracarbonyl complex while the LSIMS spectrum showed a characteristic pattern of carbonyl loss.…”

“…To investigate the scope of coordination chemistry available to this free phosphine arm, complexes 6 and 7 were reacted with a range of transition metal salts (Scheme 2) with aim of preparing a series of heteromultimetallic complexes. Reaction of complex 7 with one equivalent [AuCl(SMe) 2 ] at room temperature for 2 h resulted in the formation of the mixed Au:W complex [W(CO) 4 {N-(CH 2 PCy 2 ) 3 -j 2 P}AuCl] (8). The 31 P{ 1 H} NMR spectrum of 8 showed a characteristic high frequency shift of the uncoordinated phosphine arm from À16.9 ppm to 13.8 ppm on reaction with gold Fig.…”

“…The tripodal phosphine 1,1,1-tris(diphenylphosphinomethyl)ethane (CH 3 (CH 2 PPh 2 ) 3 , triphos, 1) is one of the most widely studied triphosphine ligands and has been shown to form an extensive range of metal complexes [4][5][6][7][8][9][10][11][12] and a number of active catalytic species [13][14][15][16][17][18]. New triphos-type ligands continue to attract interest for the preparation of coordination complexes [19][20][21][22][23][24], however, their synthesis is not always trivial.…”

Alkynyl triphosphine copper complexes: synthesis and photophysical studies

“…The reaction mixture was stirred for additional 10 h, then it was filtered, evaporated and the crude solid was recrystallized by gas-phase diffusion of pentane into a THF solution of 1 at room temperature to give pale yellow crystalline material (65 mg, 54 %). 31 Cu3(P 3 )3(1,3,5-(C2C6H4C2C6H4)3C6H3) (10). Prepared analogously to 1 using stoichimetric ratio of the reagents starting from P 3 (150 mg, 0.238 mmol), [Cu(NCMe)4](BF4) (75 mg, 0.238 mmol), 1,3,5-trisubstituted benzene (48 mg, 0.071 mmol) and KOH (13 mg, 0.232 mmol).…”

“…The crude solid was dissolved in toluene (10 mL) and precipitated with excess of pentane to give an orange solid (46 mg, 23 %). 31 …”