Formation and Reaction of P-functional Phosphanes The reaction of (me3Si)2PLi · 2 THF a (me = CH3) with PCl3 b at ?78°C via the intermediate (me3Si)2P? PCl2 1 yields [(me3Si)2P]2PCl 2 and [(me3Si)2P]2P? P(Sime3)2 3 . By addition of me3CLi c to the reaction mixture of a and b (molar ratio a:b:c (molar ratio a:b:c = 1:1:1) at ?60°C, 2 is formed as a main product, which reacts on to yield [(me3Si)2P]2PH 4 (white crystals, mp = 73°C). By reactions of a:b:c in a molar ratio of 1:1:2 the cyclotetraphosphane (me3C)3 (me3Si)P4 7 is accessible, and the additional formation of (me3Si)2PLi · 2 THF, (me3Si)3P and Li3P7 · 3 THF 13 was detected. Warming (me3Si)2P? PCl(Cme3) 5 to 20°C produces cis- and trans-cyclotetraphosphanes (me3Si)2(me3C)2P4. By running the reaction of a and b at ?78°C and adding me3CLi only after 24 h, additionally to (me3Si)2P? PH Cme3) and (me3Si)3P also (me3Si)2P? P(Cme3)? P(Cme3)? P (Sime3)2 is obtained, which is formed by metallation of (me3Si)2P? PCl(Cme3) with me3CLi and by further reaction of the intermediate (me3Si)2P? PLi(Cme3) with (me3Si)2P? PCl(Cme3). The reaction of (me3Si3)P with PCl3 at ?78°C only yields (me3Si)2P? PCl2 1 and me3SiCl. On addition of me3CLi (?78°C, molar ratio = 1:1:1) preferrably 2 and (me3Si)2P? PCl(Cme3) are formed, whereas after warming the mixture to 20°C, 4 and (me3Si)2P? PH(Cme3) are found to be the main products. These reactions are induced by the cleavage of 1 by means of me3CLi, and by the formation of (me3Si)2PLi and me3C? PCl2. 相似文献
Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VIII. Concerning the Different Tendencies of Silylated and Alkylated Phosphanes and Diphosphanes to Form Chromium Carbonyl Complexes The influence of the substituents Me3Si tBu and Me in phosphanes and diphosphanes on the formation of complex compounds with Cr(CO)5THF is investigated. tBu(Me3Si)P? P(SiMe3)2 1 and (tBu)2P? P(SiMe3)2 2, resp., react with Cr(CO)5THF 4 at ?18°C by coordinating Cr(CO)5 to the P(SiMe3)2 group to give tBu(Me3Si)P? PIV(SiMe3), · Cr(CO)5 1 a, tBu(Me3Si)PIV? PIV(SiMe3)2 · Cr(CO)4 1b and (tBu)2P? PIV(SiMe3)2 · Cr(CO)5 2a . In the reaction of 1 with 4 using a molar ratio of 1:2 at first 1 a is formed which reacts on to yield completely 1 b. In a mixture of the dissolved compounds (Me3Si)3P 5, (tBu)3P 6 and (tBu)3P? P(SiMe3)2 2 only 5 and 6 react with Cr(CO)5THF yielding (Me3Si)3P · Cr(CO)5 and (tBu)3P · Cr(CO)5, but 2 does not yet react. In a solution of (Me3Si)3P 5, P2Me4 7 and (Me3Si)2P? PMe2 3 only 5 and 7 react with Cr(CO)5THF (0.25 to 1.5 equivalents with respect to 3) to give (Me3Si)3P · Cr(CO)5, P2Me4 · Cr(CO)5 and P2Me4 · 2Cr(CO)5. The formation of complexes with Cr(CO)5THF of the phosphanes 5 and 6 is clearly favoured as compared to the silylated diphosphanes 2 and 3 (not to P2Me4); the PR2 groups (R = tBu, Me in 2 or 3 ) don't have a strong influence. 相似文献
Abstract Tris-(trimethylsilyl)phosphane and their organo substituted derivatives (Me3Si)3?nP(Me3C)n (n: 0, 1, 2) (la-c) had been found suitable for the insertion of selenium into the phosphorus-silicon bond. At deep temperatures all silylselenophosphanes of the series (Me3SiSe)3?nP(Me3Cn) (2a-c) are formed in a nearly quantitative reaction, if no excess selenium is present. (Me3C)(Me3SiSe)2P=Se (3b) and (Me3C)2(Me3SiSe)P=Se (3c) are detectable in small quantities as the only by-products of the reaction of (Ib-c), whereas (la) end in the formation of (2a) and traces of the dimer (Me3SiSe)2P-P(SeSiMe3)2 (4). On exposure to light or at elevated temperatures (2a) undergoes a disproportionation, forming Se=P(SeSiMe3)3 (3a), and the heterocycles P3Se4(SeSiMe3) (5) and α-P4Se3(SeSiMe3)2 (6). (Me3Si)2Se is spUt off as a condensation product. After further irradiation or prolonged standing at room temperature, an insoluble oligomer is formed. The constitutions of (2-6) were determined by the analysis of their 31P- and 77Se-nmr spectra. 相似文献
(Ferrocenylmethyl)phosphane ( 1 ) oxidation with hydrogen peroxide, elemental sulfur and grey selenium produced (ferrocenylmethyl)phosphane oxide 1O , sulfide 1S and selenide 1Se , respectively, as the first isolable primary phosphane chalcogenides lacking steric protection. At elevated temperatures, compound 1O disproportionated into 1 and (ferrocenylmethyl)phosphinic acid. In reactions with [(η6-mes)RuCl2]2, 1O underwent tautomerization into a phosphane complex [(η6-mes)RuCl2{FcCH2PH(OH)-κP}], whereas 1S and 1Se lost their P-bound chalcogen atoms, giving rise to the phosphane complex [(η6-mes)RuCl2(FcCH2PH2-κP)] (Fc=ferrocenyl, mes=mesitylene). No tautomerization was observed in the reaction of 1O with B(C6F5)3, which instead produced a Lewis pair FcCH2P(O)H2-B(C6F5)3. Phosphane oxide 1O added to C=O bonds of aldehydes and ketones and even to cumulenes PhNCE (E=O and S). However, both PH hydrogens were only employed in the reactions with aldehydes and cyanates. 相似文献
Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. IX. Chromium Carbonyl Complexes of Silylated and Alkylated Triphosphanes . To investigate the influence of the substituents on the formation of complex compounds of triphosphanes several derivatives were synthesized which differ in the number and position of the Me3Si and tBu groups at the primary P atoms and which bear H, Me3Si, Me of Ph groups at the secondary P atom. These are [(Me3Si)2P]2PH 1 , [(Me3Si)2P]2P(SiMe3) 2 , (MeSi)(tBu)P? P(H)? P(SiMe3)2 3 , (tBu)2P? P(SiMe3)? P(tBu)(SiMe3) 4 , [(tBu)2P]2PH 5 , [(tBu)2P]2P(SiMe3) 6 , [(Me3Si)2P]2PMe 7 , [(Me3Si)2P]2P(Ph) 8 . When reacting these compounds with Cr(CO)5THF 9 the following groups of products are obtained: Compounds 1, 3, 5, 7 and 8 at first yield products of group A and react on to B; however this second step is not important for 7 and even less for 8. Compounds 2, 4 and 6 bearing a Me3Si group at the secondary P atom yield C, but their reactivity is strongly reduced and they tend to give byproducts. Using a molar ratio of triphosphane: Cr(CO),THF 9 = 1 : 2 A forms also D in addition to B . Further reactions may occur from A and B , e. g., at 50°C 1 b ( B ) decomposes to 1 and lc (E). With Cr(CO),NBD the compounds 1, 5, 7 and 8 form products of groups E and F. At ?18°C 7 forms 7c (E) which rearranges at 75°C to 7d (F). The compounds are characterized by 31P and 1H NMR spectra, mass spectra and elemental analysis. 相似文献
The preparation of [LmAgO2CR] (L = PnBu3, P(OMe)3, P(OEt)3; m = 1, 2; R = singly-bound organic group) and [LmAg–E–AgLm] (L = PnBu3; E = oxalate; m = 1, 2, 3) is described. Their use as spin-on and CVD precursors is reported. SEM and EDX studies show that
closed and homogeneous silver films with admirable conductivity could be obtained. 相似文献
