A Comparative Study on the Structural and Chemical Properties of Group 13–15 Element Addition Compounds tBu₂PH·EX₃ (E = B, Al, Ga, In; X = Cl, Br)

Abstract

The group 13-15 element addition compounds tBu 2 PH·EX 3 (E = B, Al, Ga, In; X = Cl, Br) are accessible from the reaction of tBu 2 PH with the triel halides EX 3 (E = B, Al, Ga, In; X = Cl, Br) at room temperature. The crystal structures of the group 13-15 element addition compounds tBu 2 PH·BBr 3 (monoclinic, P2 1 /c) and tBu 2 PH·EBr 3 (E = B, Al, Ga, In) (monoclinic, P2 1 /n) are described. When the addition compound tBu 2 PH·BBr 3 was treated with one equivalent of LiN(SiMe 3 ) 2 , the reaction led to the formation of the H, 7.13 %. tBu 2 PH·AlCl 3 [1a(Al)]: 1 H NMR (300 MHz, C 6 D 6 ): δ = 1.08 (d, 3 J PH = 14.7 Hz, 18 H, tBu), 3.47 (d, 1 J PH = 324.0 Hz, PH). 13 C{ 1 H} NMR (75.5 MHz, C 6 D 6 ): δ = 30.3 (CCH 3 ), 34.3 (CCH 3 ). 31 P NMR (121.5 MHz, C 6 D 6 ): δ = 10.2 (br. m, 1 J PH = 293.0 Hz). C 8 H 19 AlCl 3 P (279.55): C, 34.37; H, 6.85. Found: C, 32.98; H, 6.16 %. tBu 2 PH·GaCl 3 [1a(Ga)]: 1 H NMR (300 MHz, C 6 D 6 ): δ = 1.03 (d, 3 J PH = 16.9 Hz, 18 H, tBu), 3.98 (d, 1 J PH = 372.3 Hz, PH). 13 C{ 1 H} NMR (75.5 MHz, C 6 D 6 ): δ = 29.3 (d, 2 J PC = 2.3 Hz, CCH 3 ), 34.3 (d, 1 J PC = 18.1 Hz, CCH 3 ). 31 P NMR (121.5 MHz, C 6 D 6 ): δ = 16.3 (br. m, 1 J PH = 376.4 Hz). C 8 H 19 GaCl 3 P (322.29): C, 29.81; H, 5.94. Found: C, 28.94; H, 5.62 %. tBu 2 PH·InCl 3 [1a(In)]: 1 H NMR (300 MHz, C 6 D 6 ): δ = 1.08 (d, 3 J PH = 11.5 Hz, 18 H, tBu), 3.25 (d, 1 J PH = 226.9 Hz, PH). 13 C{ 1 H} NMR (75.5 MHz, C 6 D 6 ): δ = 31.6 (br., CCH 3 ), 33.4 (br., CCH 3 ). 31 P NMR (121.5 MHz, C 6 D 6 ): δ = 22.3 (br. d, 1 J PH = 262.3 Hz). C 8 H 19 InCl 3 P (367.39): C, 26.15; H, 5.21. Found: C, 26.48; H, 5.32 %. Synthesis of tBu 2 PH·EBr 3 (E = B, Al, Ga, In; 1b):A flask was charged with toluene (5 mL) and triel bromides EBr 3 (BBr 3 : 0.343 g, 1.37 mmol; AlBr 3 : 0.180 g, 1.23 mmol; GaBr 3 : 0.240 g, 0.78 mmol; InBr 3 : 0.655 g, 1.85 mmol) to which was added an equimolar amount of tBu 2 PH in toluene (0.1 m solution, B: 13.4 mL; Al: 12.3 mL; Ga: 7.8 mL; In: 18.5 mL) at -78°C. Gas-phase diffusion of pentane into concentrated solutions of the addition compounds yielded colorless Xray quality crystals of tBu 2 PH·EBr 3 (E = B, Al, Ga, In; 1b). tBu 2 PH·BBr 3 [1b(B)]: Yield: 0.456 g (84 %). 1 H NMR (300 MHz, C 6 D 6 ): δ = 1.14 (d, 3 J PH = 14.4 Hz, 18 H, tBu), 4.35 (dm, 1 J PH = tBu 2 PHO·AlCl 3 [2a(Al)]: 1 H NMR (300 MHz, C 6 D 6 ): δ = 0.85 (d, 3 J PH = 17.8 Hz, 18 H, tBu), 5.73 (d, 1 J PH = 433.8 Hz, PH). 13 C{ 1 H} NMR (75.5 MHz, C 6 D 6 ): δ = 25.9 (d, 2 J PC = 2.5 Hz, CCH 3 ), 33.6 (d, 1 J PC = 18.2 Hz, CCH 3 ). 27 P NMR (121.5 MHz, C 6 D 6 ): δ = 79.2 (br. m, 1 J PH = 433.8 Hz). C 8 H 19 AlCl 3 OP (295.55): C, 32.51; H, 6.48. Found: C, 31.78; H, 6.27 %. tBu 2 PHO·GaCl 3 [2a(Ga)]: 1 H NMR (300 MHz, C 6 D 6 ): δ = 0.75 (d, 3 J PH = 14.1 Hz, 18 H, tBu), 5.56 (d, 1 J PH = 430.5 Hz, PH). 13 C{ 1 H} NMR (75.5 MHz, C 6 D 6 ): δ = 25.4 (CCH 3 ), 32.9 (CCH 3 ). 31 P NMR (121.5 MHz, C 6 D 6 ): δ = 79.7 (br. d, 1 J PH = 430.5 Hz). C 8 H 19 GaCl 3 OP (338.29): C, 28.40; H, 5.66. Found: C, 27.43; H, 5.11 %. tBu 2 PH·InCl 3 [1a(I...

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

“…Boron trihalides form 1:1 complexes with phosphine and arsine ligands, usually made by combination of the constituents in an inert solvent; hexane, benzene or toluene are the most commonly used, or sometimes in the absence of a solvent [113][114][115][116][117][118][119][120][121][122][123][124][125][126]. Table 5 lists structural data on typical examples.…”

“…During [122]. The very sterically hindered P(mesityl) 3 forms unstable adducts [AlX 3 {P(mesityl) 3 }] (X = Cl or Br), with very long Al-P bonds (see Table 6) and the solution NMR data show extensive dissociation [134].…”

An Unpredictable Reaction of tBu2PHO·BCl3 in the Presence of Water

“…Both are located on a crystallographic mirror plane. Geometric parameters ( Table 2) are in the usual ranges and compare well with three other structures containing the di-t-butylphosphonium cation, namely di-t-butylphosphonium tribromo-germanium [9], di-t-butylphosphonium tetrabromo-gallium [4], and di-t-butylphosphonium chloro-tris(pentafluorophenyl)borate [10]. Just the C-P-C bond angle is widened to 122.59(15) o due to the bulky t-butyl residues.…”

“…C 6 D 6 was dried over molecular sieves and stored under dry nitrogen. tBu 2 PHOÁBCl 3 [4] and tBu 2 PO(OH) [6] were prepared according to published procedures. The NMR spectra were recorded on a Bruker AM 250, a Bruker DPX 250, a Bruker Avance 300, and a Bruker Avance 400 spectrometer.…”

“…The gallane (tBu 2 P) 3 Ga can be synthesized from Li[PtBu 2 ] [2] and GaCl 3 [3]. Recently we have been able to prepare and to characterize the addition compounds tBu 2 PHÁEX 3 and tBu 2 PHOÁEX 3 (E = B, Al, Ga, In; X = Cl, Br, I) [4]. In the following we report about the reaction of tBu 2 PHOÁBCl 3 [5] in the presence of water in benzene at room temperature during which the phosphonium chloride [tBu 2 PH 2 ]Cl could be isolated.…”