Transition Metal Phosphido Complexes. XVII. Reactions of Silylphosphine Derivatives with (R3P)2PtCl2 (R ? Et, Ph) In reactions of (Et3P)2PtCl2 1a with LiP(SiMe3)2 at low temperatures the substitution products (Et3P)2Pt[P(SiMe3)2]Cl 2a and (Et3P)2Pt[P(SiMe3)2]2 3a are formed first. At ambient temperature from 3a P(SiMe3)3 and PEt3 are split off yielding a mixture of the diphosphene complex (Et3P)2Pt[η2-(PSiMe3)2] 4a and the phosphido-bridged platinum(I) complex [Et3PPtP(SiMe3)2]2(Pt? Pt) 5a . Heating 2a to 80°C in solution gives the P2-complex [(Et3P)2Pt]2P2 6a . 4a and 6a are also obtained reacting 1a with [(Me3Si)2P]2. From 1a and [Me3Si(Me3C)P]2 the diphosphene complex (Et3P)2Pt[η2-(PCMe3)2] 8a is available. In the reaction of 1a with (Me3Si)2P? P(CMe3)SiMe3 the formation of the asymmetric diphosphene complex (Et3P)2Pt[η2-Me3SiP?PCMe3] 9a can be proved n.m.r. spectroscopically. Analogous reactions of (Ph3P)2PtCl2 1b with LiP(SiMe3)2, and with [Me3Si(Me3C)P]2 are much more difficult to survey. The complexes (Ph3P)2Pt[η2-(PSiMe3)2] 4b , [(Ph3P)2Pt]2P2 6b , and (Ph3P)2Pt[η2-(PCMe3)2] 8b are formed in n.m.r. spectroscopically detectable amounts but could not be isolated as pure compounds. N.m.r. and mass spectral data are reported. 相似文献
Synthesis and Reactivity of the Diphenylphosphanyltrimethylsilylamine Ph2PN(H)SiMe3 The trimethylsilyliminotriphenylphosphoran Ph3P=NSiMe3 ( 1 ) reacts with sodium in THF under cleavage of one P–Cphenyl bond leading to the PIII‐species [(THF)3Na(Ph2PNSiMe3)] ( 2 ). Reaction with NH4Br or hydrolysis with water gives the diphenylphosphanyltrimethylsilylamine Ph2PN(H)SiMe3 ( 3 ) and in low yields the oxidized byproduct [(THF)Na(OOPPh2)]n ( 4 ) that can be synthesised directly in high yields in the reaction of Ph2POOH and NaH in THF. 3 was reacted with an equimolar amount of Zn{N(SiMe3)2}2 to give [(Me3Si)2NZnPh2PNSiMe3]2 ( 5 ). 3 reacts with caesium under phosphorus‐phosphorus bond formation in a reductive substituent coupling reaction to give [(THF)Cs2{Ph(NSiMe3)P}2]n ( 6 ) where phosphorus(III) is reduced to phosphorus(II). Phosphorus‐phosphorus bond formation to give (Ph2PNSiMe3)2 ( 7 ) where the phosphorus(III) centres are oxidized to PIV is observed in the reaction of 3 with n‐BuLi and bismuthtrichloride. 相似文献
Half-sandwich dibenzyl complexes of scandium have been prepared by stepwise treatment of scandium trichloride with lithium derivatives of silyl-functionalized tetramethylcyclopentadienes (C5Me4H)SiMe2R (R = Me, Ph) and benzyl magnesium chloride. The resulting complexes [Sc(η5-C5Me4SiMe3)(CH2Ph)2(THF)] and [Sc(η5-C5Me4SiMe2Ph)(CH2Ph)2(1,4-dioxane)] show structure related to that of the corresponding bis(trimethylsilylmethyl) compounds [Sc(η5-C5Me4SiMe2R)(CH2SiMe3)2(THF)]. The four-coordinate complexes display η1-coordinated benzyl ligands without significant interaction of the ipso-carbon of the phenyl moiety. Conversion of [Sc(η5-C5Me4SiMe3)(CH2Ph)2(THF)] into the cationic species by treatment with triphenylborane in THF led to the formation of a stable charge separated complex [Sc(η5-C5Me4SiMe3)(CH2Ph)(THF)x][BPh3(CH2Ph)]. Benzyl cation formed using [Ph3C][B(C6F5)4] in toluene resulted in a moderately active syndiospecific styrene polymerization catalyst. 相似文献
Synthesis and Characterization of a New Metallacyclic Compound of Osmium The bissilylated phosphorane, Me3SiNP(Ph2)CH2(Ph2)PNSiMe3 1 reacts with OsO4 via the migration of SiMe3 groups to give a new metallacycle 2 containing OsVIII. 1H, 31P, and 29Si n.m.r. spectroscopic investigations confirm the cyclic structure of 2 . 相似文献
During studies of the reactions of ─N(H)SiMe3 and ─N(Me)SiMe3 derivatives of Cl3PNSO2Cl with acetonitrile and BCl3 we have obtained six-membered polyheteroatomic cycles ?P(Cl2)NSO2(Cl)N(H) C(Me)N? and ?P(Cl2)NS(O)(Cl)OB(Cl2)N(Me)?.1, 2 In the system Ph2PCl3, H2NSO2Cl and HN(SiMe3)2 we have identified and isolated several P─N─S cycles, e.g. the reaction of Ph2PCl3 with H2NSO2Cl gives Ph2ClPNSO2Cl3 which with HN(SiMe3)2 reacts to ?S(O2)N(H)P(Ph)2N(H)SO2N(H)P(Ph)2N(H)?, ?S(O2)N(H)S(O2)N(H)P(Ph)2N(H)P(Ph)2N(H)? and ?[S(O2)N(H) P(Ph)2NP(Ph)2N(H)]+? Cl?; Ph2PCl3 with HN(SiMe3)2 gives N[P(Ph)2N(H)SiMe3]2+ Cl?, and H2NSO2Cl with HN(SiMe3)2 leads to SO2(NHSiMe3)2. The reaction of Ph2PCl3 with HN(SiMe3)2 gives N(P(Ph)2NHSiMe3)2Cl in a very good yield which was further used to syntheses of metal-containing heterocycles. By the reaction of N[P(Ph)2N(H)SiMe3]2+Cl? with some covalent halogenides we have obtained six-membered heterocycles containing B, As, In, and Sn. The same cyclic compounds can also obtained by the reaction of N[P(Ph2)NH2]2+Cl? or HN(P(R2)N(H)SiMe3)2 with covalent halogenides.4?6 However, the synthetic route via N[P(Ph)2NHSiMe3]2+Cl? is more convenient and gives the compounds in almost quantitative yields. The identity of all compounds was unambiguously establised by their X-ray structure determination. 相似文献
Homoleptic Amides of Zinc, Cadmium, and Mercury ZnCl2, CdCl2 and HgCl2 react with the lithium salts ( 1 a–5 a ) of the sterically demanding secundary amines HN(SiMe3)Ph ( 1 ), HN(SiMe3)C6H3Me2‐2,6 ( 2 ), HN(SiMe3)C6H3iPr2‐2,6 ( 3 ), HN(SiMe3)C6H3tBu2‐2,5 ( 4 ), and HN(SiMe2NMe2)C6H3iPr2‐2,6 ( 5 ) yielding the corresponding homoleptic metal amides Zn[N(SiMe2R′)R]2 ( 1 b–5 b ), Cd[N(SiMe2R′)R]2 ( 1 c , 5 c ), and Hg[N(SiMe2R′)R]2 ( 1 d–5 d ), respectively. Except the dimeric {Zn[N(SiMe3)Ph]2}2 ( 1 b ), all complexes are monomeric. The compounds were characterized by elemental analyses, molecular weight determinations, NMR and mass spectra. Furthermore, the zinc amides ( 1 b–5 b ) and the mercury amides 1 d–3 d and 5 d were characterized by single crystal X‐ray structure analysis. Except 1 b and 5 b , they show a linear N–M–N arrangement. 相似文献
Synthesis and Structure of C,N‐difunctionalized Sulfinimideamides Sulfurdiimides RN=S=NR ( 1 a , b ) react in diethyl ether with two equivalents of lithiummethyl to give dimeric C,N‐dilithiummethylenesulfinimideamide ether adducts {Li2[H2C–S(NR)2 · Et2O]}2 ( 2 a , b ) ( a : R = tBu, b : R = SiMe3). Metathesis of 2 b with four equivalents of Me3SiCl, Me3SnCl or Ph3SnCl yields the corresponding C,N‐bis‐substituted sulfinimideamides R3EH2C–S[N(SiMe3)2]NER3 ( 3 – 5 ) ( 3 : R = Me, E = Sn; 4 : R = Ph, E = Sn; 5 : R = Me, E = Si). The crystal structures of 2 a and 2 b were determined by X‐ray structure analysis. Both compounds form centrosymmetric cage structures consisting of two distorted face sharing cubes ( 2 a : space group P1 (No. 2); Z = 2 (4 · 0,5); 2 b : space group C2/c (No. 15), Z = 4). 相似文献
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXII. The Formation of [η2‐{tBu–P=P–SiMe3}Pt(PR3)2] from (Me3Si)tBuP–P=P(Me)tBu2 and [η2‐{C2H4}Pt(PR3)2] (Me3Si)tBuP–P = P(Me)tBu2 reacts with [η2‐{C2H4}Pt(PR3)2] yielding [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]. However, there is no indication for an isomer which would be the analogue to the well known [η2‐{tBu2P–P}Pt(PPh3)2]. The syntheses and NMR data of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] and [η2‐{tBu–P=P–SiMe3}Pt(PMe3)2] as well as the results of the single crystal structure determination of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] are reported. 相似文献
Metal Complexes of Dyes. Phosphine-Nickel, Palladium, Platinum Complexes and Pentamethylcyclopentadienyl Rhodium and Iridium Complexes of 2,2′-Dihydroxyazoarenes The terdentate dianions of 2,2′-dihydroxyazobenzene (L1H), 1-(2-hydroxy-4-nitrophenylazo)-2-naphthol (L2H), 1-(2-hydroxy-5-nitrophenylazo)-2-naphthol (L3H) and 1-phenyl-3-methyl-4-(2-hydroxy-5-nitrophenylazo)-5-pyrazolone (L4H) form with chloro bridged complexes [(R3P)MCl2]2 (M = Pd, Pt; R = Ph, nBu), [(n5-C5Me5)MCl2]2 (M = Rh, Ir) and with (nBu3P)2NiCl2 the metal dye complexes (R3P)ML (M = Ni, Pd, Pt) and (C5Me5)ML (M = Rh, Ir). The structures of (Ph3P)PtL1 and (nBu3P)PdL3 have been determined by X-ray diffraction. For the complexes (n5-C5Me5)ML (M = Rh, Ir) with asymmetric metal centers two diastereoisomers are detected by nmr spectroscopy which points to the ?hydrazone”? form of the azo ligand with a pyramidalized N-atom. 相似文献
On the Reactivity of (η5-C5Me5)(CO)2FeP(SiMe3)2 Toward P-Chloromethylene phosphanes The reaction of (η5-C5Me5)(CO)2FeP(SiMe3)2 ( 2 ) with three equivalents of Cl? P?C(SiMe3)2 ( 3a ) afforded the 3-methanediyl-1,3,5,6-tetraphosphabicyclo[3.1.0]hex-2-ene (η5-C5Me5)(CO)2Fe? ( 6a ). In contrast, 2 reacts with two equivalents of Cl? P?C(Ph)SiMe3 ( 3b ) to give the thermolabile (η5-C5Me5) · (CO)2Fe? P[P?C(Ph)SiMe3]2 ( 4b ) which decomposed during the reaction with further 3b. 4 b was also obtained from (η5-C5Me5)(CO)2Fe? P(SiMe3)? P?C(SiMe3)2 ( 1a ) and two equivalents of 3b . 相似文献
Investigations on the Formation of Silylated iso-Tetraphosphanes We investigated the formation of iso-tetraphosphanes by reacting [Me(Me3Si)P]2PCl 4 , Me(Me3Si)P? P(Cl)? P(SiMe3)2 8 , Me(Me3Si)P? P(Cl)? P(SiMe3)(CMe3) 9 , [Me(Me3Si)P]2PCl 20 , Me3C(Me3Si)P? P(Cl)? P(SiMe3)2 21 , and [MeC(Me3Si)P]2PCl 22 with LiP(SiMe3)Me 1 , LiP(SiMe3)2 2 , and LiP(SiMe3)CMe3 3 , respectively, to elucidate possible paths of synthesis, the influence of substituents (Me, SiMe3, CMe3) on the course of the reaction, and the properties of the iso-tetraphosphanes. These products are formed via a substitution reaction at the P2Cl group of the iso-triphosphanes. However, with an increasing number of SiMe3 groups in the triphosphane as well as in reactions with LiP(SiMe3)Me, cleaving and transmetallation reactions become more and more important. The phosphides 1,2, and 3 attack the PC1 group of 4 yielding the iso-tetraphosphanes P[P(SiMe3)Me]3 5, [Me(Me3Si)P]2P? P(SiMe3)2 6 and [Me(Me3Si)P]2P? P(SiMe3)CMe3 7. I n reactions With 8 and 9, LiP(SiMe3)Me causes bond cleavage and mainly leads to Me(Me3Si)P? P(Me)? P(SiMe3)2 13 and Me(Me3Si)P? (Me)? P(SiMe3)CMe3 16, resp., and to monophosphanes; minor products are [Me(SiMe3)P]2P? P(SiMe3)2 6 and [Me(Me2Si)P]2P? P(SiMe3)CMe2 7. LiP(SiMe3)2 2 and LiP(SiMe3)CMe2 3 with 8 and 9 give Me(Me3,Si)P? P[P(SiMe3)2]2 10, Me(Me2Si)P? P[P(SiMe3)CMe2]? P(SiMe3)2 11, and Me(Me3Si)P? P[P(SiMe3)CMe3]2 12 as favoured products. With 20, LiP(SiMe3)2 2 forms P[P(SiMe3)2]3 28. Bond cleavage products are obtained in reactions of 20 with 1 and 2, of 21 with 1, 2, and 3, and of 22 with 1 and 2. P[P(SiMe3)CMe3]3 23 is the main product in the reaction of 22 with LiP(SiMe3)CRle2 3. In the reactions of 22 with 1, 2, and 3 the cyclophosphanes P3(CMe3)2(SiMe3)25, P4[P(SiMe3)CMe3]2(CMe3)2 26, and P5(CMe3)4(SiMe3) 27 are produced. The formation of these rom- pounds begins with bond cleavage in a P- SiMe, group by means of the phosphides. The thermal stability of the iso-tetraphosphanes decreases with an increasing number of silyl groups in the molecule. At 20O°C compounds 5, 7, and 23 are crystals; also 6 is stable; however, 10, It, 12, and 28 decompose already. 相似文献
Synthesis and Properties of Partially Silylated Tri- and Tetraphosphanes. Reaction of Lithiated Diphosphanes with Chlorophosphanes The reactions of Li(Me3Si)P? P(SiMe3)(CMe3) 1 , Li(Me3Si)P? P(CMe3)2 2 , and Li(Me3C)P? P(SiMe3)(CMe3) 3 with the chlorophosphanes P(SiMe3)(CMe3)Cl, P(CMe3)2Cl, or P(CMe3)Cl2 generate the triphosphanes [(Me3C)(Me3Si)P]2P(SiMe3) 4 , (Me3C)(Me3Si)P? P(SiMe3)? P(CMe3)2 6 , [(Me3C)2P]2P(SiMe3) 7 , and (Me3C)(Me3Si)P? P(SiMe3)? P(CMe3)Cl 8 . The triphosphane (Me3C)2P? P(SiMe3)? P(SiMe3)2 5 is not obtainable as easily. The access to 5 starts by reacting PCl3 with P(SiMe3)(CMe3)2, forming (Me3C)2 P? PCl2, which then with LiP(SiMe3)2 gives (Me3C)2 P? P(Cl)? P(SiMe3)2 11 . Treating 11 with LiCMe3 generates (Me3C)2P? P(H)? P(SiMe3)2 16 , which can be lithiated by LiBu to give (Me3C)2P? P(Li)? P(SiMe3)2 13 and after reacting with Me3SiCl, finally yields 5 . 8 is stable at ?70°C and undergoes cyclization to P3(SiMe3)(CMe3)2 in the course of warming to ambient temperature, while Me3SiCl is split off. 7 , reacting with MeOH, forms [(Me3C)2P]2PH. (Me3C)2P? P(Li)? P(SiMe3)2 18 , which can be obtained by the reaction of 5 with LiBu, decomposes forming (Me3C)2P? P(Li)(SiMe3), P(SiMe3)3, and LiP(SiMe3)2, in contrast to either (Me3C)2P? P(Li)? P(SiMe3)(CMe3) 19 or [(Me3C)2P]2PLi, which are stable in ether solutions. The Li phosphides 1 , 2 , and 3 with BrH2C? CH2Br form the n-tetraphosphanes (Me3C)(Me3Si)P? [P(SiMe3)]2? P(SiMe3)(CMe3) 23 , (Me3C)2P? [P(SiMe3)]2? P(CMe3)2 24 , and (Me3C)(Me3Si)P? [P(CMe3)]2? P(SiMe3)(CMe3) 25 , respectively. Li(Me3Si)P? P(SiMe3)2, likewise, generates (Me3Si)2P? [P(SiMe3)]2? P(SiMe3)2 26 . Just as the n-triphosphanes 4 , 5 , 6 , and 7 , the n-tetraphosphanes 23 , 24 , and 25 can be isolated as crystalline compounds. 23 , treated with LiBu, does nor form any stable n-tetraphosphides, whereas 24 yields (Me3C)2P? P(Li)? P(SiMe3)? P(CMe3)2, that is stable in ethers. With MeOH, 24 , forms crystals of (Me3C)2P? P(H)? P(SiMe3)? P(CMe3)2. 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
Lithiated Siloxy-silylamino-silanes — Preparation and Reactions with Chlorodimethylsilane The siloxy-silylamino-silanes (Me3SiO)Me3–nSi(NHSiMe3)n ( 1 : n = 1, 2 : n = 2, 3 : n = 3) are obtained by coammonolysis of the chlorosiloxysilanes (Me3SiO)Me3–nSiCln (n = 1–3) with chlorotrimethylsilane. The reaction of 1, 2 , and 3 with n-butyllithium in appropriate molar ratio in n-hexane gives the siloxy-silylamido-silanes (Me3SiO)Me3–nSi(NLiSiMe3)n ( 4 : n = 1, 5 : n = 2, 6 : n = 3), which were spectroscopically characterized (IR, 1H-, 7Li-, 29Si-NMR) and allowed to react in solution (n-hexane, THF) with Me2Si(H)Cl. 4 reacts to the N-substitution product (Me3SiO)Me2SiN(SiMe3)SiMe2H 7, 5 to (Me3SiO)MeSi[N(SiMe3)SiMe2H](NHSiMe3) 8 , (Me3SiO)MeSi[N(SiMe3)SiMe2H]2 9 and to the cyclodisilazane 10. 6 gives in THF the cyclodisilazanes 11 : R = H; 12 : R = HMe2Si) and ( 13 , in n-hexane only 11 in small amounts. An amide solution of 2 with n-butyllithium in the molar ratio 1:1 in n-hexane leads to 8 (main product), 2 and 10; in THF 10 and 2 are obtained nearly in same amounts and 8 and 9 as byproducts. The amide solutions of 3 with n-butyllithium in the molar ratio 1:1 and 1:2, resp., show nearly the same behaviour in n-hexane and THF. In THF 3, 11 , and 12 and in n-hexane 3, 11, 12 , and (Me3SiO)Si[N(SiMe3)SiMe2H](NHSiMe3)2 14 are formed. 相似文献
Reactions of some Methylmetal Halides of Aluminium, Gallium, and Indium with Hexamethyldisilazane MeAlCl2 or MeGaBr2, and bis(trimethylsilyl)amine form the dimeric, mixed-substituted ring molecules (Me(Hal)MIII–N(H)SiMe3)2 and one equivalent Me3SiHal. The NMR (1H, 13C, 29Si) and vibrational spectra (IR, Raman) are measured and the X-ray structure analysis of the compound with MIII = Al and Hal = Cl, has been done as well. Me2AlCl with an excess of HN(SiMe3)2 forms the expected amide (Me2Al–N(H)SiMe3)2, the homologue Me2GaCl with HMDS, however, gives at 50–55 °C only the cyclic (1 : 1) adduct (Me2Ga–N(H)SiMe3) · (Me2GaCl). This complex crystallizes in the space group Cmc21, the unit cell consists of four binucleate molecules with folded Ga–N–Ga–Cl-ring skeletons. 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
This work describes the synthesis and full characterization of a series of GaCl3 and B(C6F5)3 adducts of diazenes R1?N?N?R2 (R1=R2=Me3Si, Ph; R1=Me3Si, R2=Ph). Trans‐Ph?N?N?Ph forms a stable adduct with GaCl3, whereas no adduct, but instead a frustrated Lewis acid–base pair is formed with B(C6F5)3. The cis‐Ph?N?N?Ph ? B(C6F5)3 adduct could only be isolated when UV light was used, which triggers the isomerization from trans‐ to cis‐Ph?N?N?Ph, which provides more space for the bulky borane. Treatment of trans‐Ph?N?N?SiMe3 with GaCl3 led to the expected trans‐Ph?N?N?SiMe3 ? GaCl3 adduct but the reaction with B(C6F5)3 triggered a 1,2‐Me3Si shift, which resulted in the formation of a highly labile iso‐diazene, Me3Si(Ph)N?N; stabilized as a B(C6F5)3 adduct. Trans‐Me3Si?N?N?SiMe3 forms a labile cis‐Me3Si?N?N?SiMe3 ? B(C6F5)3 adduct, which isomerizes to give the transient iso‐diazene species (Me3Si)2N?N ? B(C6F5)3 upon heating. Both iso‐diazene species insert easily into one B?C bond of B(C6F5)3 to afford hydrazinoboranes. All new compounds were fully characterized by means of X‐ray crystallography, vibrational spectroscopy, CHN analysis, and NMR spectroscopy. All compounds were further investigated by DFT and the bonding situation was assessed by natural bond orbital (NBO) analysis. 相似文献
Concerning the Thermal Behaviour of Partially Silylated Tri- and Tetraphosphanes The influence of Me3Si- and Me3C-substituents in the compounds (Me3Si)P[P(SiMe3)(CMe3)]2 1 , (Me3C)2P-P(SiMe3)? P(SiMe3)2 2 , (Me3C)2P? P(SiMe3)? P(SiMe3)(CMe3) 3 , (Me3Si)P[P(CMe3)2]2 4 , (Me3C)(Me3Si)P? [P(SiMe3)]2? P (SiMe3)(CMe3) 5 , (Me3C)(Me3Si)P? [P(CMe3)]2? P (SiMe3)(CMe3) 6 and (Me3C)2P? [P(SiMe3)]2? P (CMe3)2 7 on their thermal stability as well as on the reactions that occur, when these compounds are exposed to higher temperatures, is investigated. The tetraphosphane 6 , bearing 4 Me3C and 2 Me3Si groups (the latter being located at the primary P atoms) hardly shows any changes, when it is exposed to 100°C in toluene (hermetically sealed ampoule) for several days, while the remaining compounds are found to rearrange significantly under similar conditions. Thus 1 [no (Me3C)2P-group] forms trans- P4 (SiMe3)2(CMe3)2 9 , while (Me3C)P(SiMe3)2 8 is being cleaved off, which can be understood easily, assuming the formation of the corresponding linear pentaphosphane (accompanied by the cleave-off of 8 ) and its subsequent cyclisation to 9 (again splitting off 8 ). 5 is found to form cyclophosphanes (tri-, penta-, hexa-), while (Me3C)P(SiMe3)2 and P(SiMe3)3 are being cleaved off. All of the remaining compounds mentioned [with (Me3C)2P-groups] finally yield, aside of P(SiMe3)3 and (Me3C)P(SiMe3)2, the cyclophosphanes P4[P(CMe3)2]4 11 and P3[P(CMe3)2]3 12 , which can be explained by the formation of the reactive intermediate (Me3C)2P? \documentclass{article}\pagestyle{empty}\begin{document}$\mathop {\rm P}\limits_ - ^ - $\end{document} ( which, however, has not been proven). 相似文献
Crystal Structure of Bis[lithium-tris(trimethylsilyl)hydrazide] and Reactions with Fluoroboranes, -silanes, and -phospanes Tris(trimethylsilyl)hydrazine reacts with n-butyllithium in n-hexane to give the lithium-derivative 1 . The reaction of 1 with SiF4, PhSiF3, BF3 · OEt2, F2BN(SiMe3)2 and PF3 leads to the substitution products 2–6 . The 1,2-diaza-3-bora-5-silacyclopentane 7 is formed by heating (Me3Si)2N? N(SiMe3)(BFNSiMe3)2 ( 5 ) at 250°C. In the reaction of (Me3Si)2N? N(SiMe3)PF2 ( 6 ) with lithiated tert.-butyl(trimethylsilyl)amine the hydrazino-iminophosphene (Me3Si)2N? N = P? N(SiMe3)(CMe3) ( 8 ) is obtained. In the molar ratio 2:1 1 reacts with SiF4 and BF3 · OEt2 to give bis[tris(trimethylsilyl)hydrazino]silane 9 and -borane 10 . 相似文献
Stannylation Experiments with NH-functional Aminoiminophosphoranes. Synthesis and Structure of the Tricyclic Stannaphosphazenes [Me2Sn(tBu2PN)NH]2 and [nBu2Sn(Ph2PN)2NH]2 Aminoiminophosphoranes tBu2P(NH)NH2 ( 1 ) and (H2NPPh2)N(Ph2PNH) ( 2 ) react with diaminostannanes R2Sn(NEt2)2 by cyclocondensation to give cyclostannaphosphazenes [Me2Sn(tBu2PN)NH]2 ( 3 ) and [R2Sn(Ph2PN)2NH]2 ( 4 a , b ) ( a : R = Me, b : R = nBu). With 2 and Me3SnNEt2 the ring compound Me2Sn(Ph2PN)2NSnMe3 ( 5 ) besides Me4Sn is formed by per-N-stannylation and Sn-methyl group transfer. The crystal structures of 3 and 4 b were determined by X-ray structure analysis. 3 forms a planar heterotricyclus containing three four-membered rings with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1). 4 b consists of a tricyclic molecule with two puckered six-membered rings and one planar four membered tin-nitrogen ring with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1). 相似文献
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