Das F₃SiPH₂

Abstract

F3SiPH2 wird nach Gl.(1) in Ausbeuten um 60% gebildet, während Br2SiF2 und Br3SiF auf Grund von Dismutationen nicht zu den entsprechenden Silylphosphinen führen. Es werden die NMR‐ und IR‐Daten mitgeteilt. F3SiPH2 wird von HE(CF3)2 (E = P, As) nicht gespalten. während es mit JE(CF3)2 nach Gl.(2) analog dem H3SiPH2 reagiert. Auf Grund geringerer Basizität des P‐Atoms im F3SiPH2 reagiert es langsamer als H3SiPH2. Die mit BCl3, BBr3, AlCl3 entstehenden Addukte sind weniger beständig als die des H3SiPH2. Demzufolge wird H3SiPH2 leichter gespalten als F3SiPH2.

Lithium, Sodium, and Copper(I) Supersilylphosphanediides M2PSitBu3: Compounds with Novel Spherical (M2P)n Frameworks

“…These reactions lead smoothly (Scheme 1) at increased temperature (Me 3 SiCl) or at room temperature (Me 3 SnCl) to the compounds R*PH(EMe 3 ) and R*P(EMe 3 ) 2 , whose composition conversely allows conclusions about the number of alkali metal atoms in the used phosphanides and phosphanediides. A further reaction (Scheme 1) which demonstrates the suitability of the compounds obtained as phosphanide transfer agents [1] is that of CuI and 1 b (and probably also 3 c) with metal exchange to give the air-and moisture-stable dicopper phosphanediide 3 d. This compound, which crystallizes as yellow-green prisms, could not be characterized by NMR spectroscopy because of its insolubility in organic solvents such as THF or benzene; however, the crystals were suitable for an X-ray structure analysis (see below).…”

“…Colorless, microcrystalline, air-and moisture-sensitive, oligomeric dilithium supersilylphosphanediide 3 b, which is insoluble in pentane and sparingly soluble in benzene and toluene, also precipitated as microcrystals on cooling of toluene solutions; however, these crystals were not suitable for X-ray structure analysis. 1 very broad signal (h 1/2 1243 Hz) with five maxima at d À 395.5, À 397.0, À 400.0, À 404.5, À 406.5; 7 Li NMR (C 6 D 6 , LiCl in D 2 O external): d 6.6 (h 1/2 130 Hz; Li 2 PR*). Notes: 1) According to NMR spectroscopy (C 6 D 6 ), after Li 2 PR* (0.230 g, 0.94 mmol) and Me 3 SiCl (4.0 mmol) in C 6 D 6 (1 mL) had been heated to 100 8C for three days, complete conversion had occurred to supersilylbis(trimethylsilyl)phosphane R*P(SiMe 3 ) 2 , which, after removal of insoluble components and volatile components, remained as a colorless, air-and moisture-sensitive solid.…”

“…60 %), which according to preliminary X-ray structure analytical studies contained tetramers (from benzene) and hexamers (from toluene), respectively, of lithium supersilylphosphanide 1 a. 1 Hz; LiHPR*). Notes: 1) LiHPR* (0.225 g, 0.950 mmol) and Me 3 SiCl (4.0 mmol) were heated to 60 8C for 24 h in C 6 D 6 (1 mL).…”

“…According to NMR spectroscopy complete conversion to supersilyltrimethylsilane R*PHSiMe 3 had taken place, which, after removal of soluble components and volatile components, remained as a colorless, air-and moisture-sensitive solid. 1 3) LiHPR* reacted with tBu 2 HSiF and tBu 2 SiF 2 to give R*PHSiHtBu 2 and R*PHSiFtBu 2 , respectively. [18] 1 b: NaR* (2.15 mmol) [19] in THF (5 mL) was added to R*PH 2 (0.500 g, 2.15 mmol) [18] in THF (3 mL).…”

“…Dark red needles of dimeric sodium supersilylphosphanide tetrahydrofuran (1/2) (1 b) precipitated from this solution in the course of five days at À 25 8C after addition of n-pentane (1 mL) (conversion to R*PHSiMe 3 and R*PHSnMe 3 is possible by reaction with Me 3 SiCl and Me 3 SnCl, see 1 a). 1 . According to X-ray structure analysis [2] 1 b contains a planar NaPNaP four-membered ring (NaÀP 2.840(4) , Na-P-Na/P-Na-P 85.7(1)/94.3(1)8) with distorted tetrahedrally coordinated P (2 Na H R*) and Na atoms (2 P 2 THF) as well as trans-oriented R* groups (PÀSi 2.197(3), NaÀO 2.281 (7), NaÀO 2.330 (8) ; O-Na-O 91.5(3)8).…”