共查询到20条相似文献,搜索用时 15 毫秒
1.
Garcia F Goodman JM Kowenicki RA McPartlin M Riera L Silva MA Wirsing A Wright DS 《Dalton transactions (Cambridge, England : 2003)》2005,(10):1764-1773
The 1 : 1 reactions of [ClP(mu-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(mu-NtBu)2(1-Y-2-HN-C6H4)]2, predominantly as the cis isomer in the case of Y=O (1.cis) and as the trans isomer for Y=S (2.trans). Model M.O. calculations suggest that the selection of the cis and trans isomers is not thermodynamically controlled. The alternative isomers 1.trans and 2.cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H4)P(mu-NtBu)]2[Y=O (3), S (4)] with nBuLi followed by cyclisation with [ClP(mu-NtBu)]2. The solid-state structures of 1.cis/trans(50 : 50), 2.cis, 3 and 4 are reported. 相似文献
2.
Dodds F García F Kowenicki RA McPartlin M Riera L Steiner A Wright DS 《Chemical communications (Cambridge, England)》2005,(40):5041-5043
The tetrameric macrocycle [(P(mu-NtBu))2(1,4-(NH)2C6H4)]4, obtained from the reaction of the phosphazane dimer [ClP(mu-NtBu)]2 with p-phenylenediamine, has an unusual folded conformation in the solid state and contains a roughly tetrahedral arrangement of endo N-H groups for the potential coordination of anions. 相似文献
3.
Dodds F García F Kowenicki RA Parsons SP McPartlin M Wright DS 《Dalton transactions (Cambridge, England : 2003)》2006,(35):4235-4243
The condensation reactions of the dimer [ClP(micro-NR)](2) with organic diacids [LL(H)(2)], possessing linear orientations of their organic groups, result in the formation of phospha(III)zane macrocyles of the type [{P(mu-NR)}(2)(LL)](n) of various sizes. The series of macrocycles [{P(mu-N(t)Bu)}(2){1,5-(NH)(2)C(10)H(6)}](3), [{P(mu-NCy)}(2)(1,5-O(2)C(10)H(6))](n) [n = 3; n = 4], [{P(mu-N(t)Bu)}(2){1,4-(NH)(2)C(6)H(4)}](4), [{P(mu-N(t)Bu)}(2)(1,4-O(2)C(6)H(4))], [{P(mu-NCy)}(2)(1,4-O(2)C(6)H(4))](3) and [{P(mu-N(t)Bu)}(2){(NH)C(6)H(4)OC(6)H(4)(NH)}](2) can be related to classical organic frameworks, like calixarenes. 相似文献
4.
The reaction of [ClP(muNtBu)2PNtBuH] (1) with LiBsBu3H yields trans-[HP(muNtBu)2PNtBuH] (2), by contrast, reaction with LiBEt3H yields cis-[HP(mu-NtBu)2PNtBuH] (3). Compounds and represent the first examples of P-H-functionalised cyclophosph(III)azanes. Deprotonation of with BnNa (Bn=benzyl) gives the first example of a secondary phosphine-functionalised cyclodiphosph(III)azane anion [HP(mu-NtBu)2PNtBu]- (4). 相似文献
5.
García F Goodman JM Kowenicki RA Kuzu I McPartlin M Silva MA Riera L Woods AD Wright DS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(23):6066-6072
The structures of the host-guest complexes [[[[P(mu-NtBu)]2(mu-NH)]5]I]-.[Li(thf)4]+ [2.I[Li(thf)4]] and [[[P(mu-NtBu)]2(mu-NH)]5].HBr.THF (2.HBr.THF) show that increased distortion of the framework of the pentameric macrocycle [[[P(mu-NtBu)]2(mu-NH)]5] (2) occurs with the larger halide ions. Theoretical studies show that the thermodynamic stabilities of the model host-guest anions [2.X]- (X=Cl, Br, I) are in the order Cl- approximately Br->I-, that is, the reverse of the templating trend observed experimentally. These studies support the view that the selection of the pentamer 2 over the tetramer [[[P(mu-NtBu)]2(mu-NH)]4] (1) is kinetically controlled, a conclusion which is also consistent with the previous observation that the frameworks of 1 and 2 are not in dynamic equilibrium with each other. 相似文献
6.
The ambidentate dianions [(t)BuN(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu](2)(-) (5a, E = S; 5b, E = Se) are obtained as their disodium and dipotassium salts by the reaction of cis-[(t)Bu(H)N(E)P(mu-N(t)Bu)(2)P(E)N(H)(t)Bu] (6a, E = S; 6b, E = Se), with 2 equiv of MN(SiMe(3))(2) (M = Na, K) in THF at 23 degrees C. The corresponding dilithium derivative is prepared by reacting 6a with 2 equiv of (t)BuLi in THF at reflux. The X-ray structures of five complexes of the type [(THF)(x)()M](2)[(t)BuN(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu] (9, M = Li, E = S, x = 2; 11a/11b, M = Na, E = S/Se, x = 2; 12a, M = K, E = S, x = 1; 12b, M = K, E = Se, x = 1.5) have been determined. In the dilithiated derivative 9 the dianion 5a adopts a bis (N,S)-chelated bonding mode involving four-membered LiNPS rings whereas 11a,b and 12a,b display a preference for the formation of six-membered MNPNPN and MEPNPE rings, i.e., (N,N' and E,E')-chelation. The bis-solvated disodium complexes 11a,b and the dilithium complex 9 are monomeric, but the dipotassium complexes 12a,b form dimers with a central K(2)E(2) ring and associate further through weak K.E contacts to give an infinite polymeric network of 20-membered K(6)E(6)P(4)N(4) rings. The monoanions [(t)Bu(H)N(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu)](-) (E = S, Se) were obtained as their lithium derivatives 8a and 8b by the reaction of 1 equiv of (n)BuLi with 6a and 6b, respectively. An X-ray structure of the TMEDA-solvated complex 8a and the (31)P NMR spectrum of 8b indicate a N,E coordination mode. The reaction of 6b with excess (t)BuLi in THF at reflux results in partial deselenation to give the monolithiated P(III)/P(V) complex [(THF)(2)Li[(t)BuN(Se)P(mu-N(t)Bu)(2)PN(H)(t)Bu]] 10, which adopts a (N,Se) bonding mode. 相似文献
7.
Bond AD Doyle EL García F Kowenicki RA Moncrieff D McPartlin M Riera L Woods AD Wright DS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(9):2271-2276
The unique structure of [(tBuN)(2)PK]( infinity ) (2) (containing [(tBuN)(2)P](-) monoanions) is in stark contrast to the previously reported Li(+) analogue [[[tBuNP(mu-NtBu)](2)](2)]Li(4) (1) (containing the dimeric [[tBuNP(mu-NtBu)](2)](2-) ion). DFT and (31)P NMR spectroscopic studies reveal that the formation of the monoanion arrangements are most thermodyamically favored for Li, Na, and K, 1 being the product of kinetic control and 2 being the product of thermodynamic control. 相似文献
8.
9.
10.
Chan WT Eisler D García F Gonzalez-Calera S McPartlin M Morey JV Mulvey RE Singh S Steiner A Wright DS 《Chemical communications (Cambridge, England)》2008,(19):2251-2253
The hydrolysis of [ClP(mu-NtBu)]2 with H2O-Et3N in thf, followed by in situ lithiation with nBuLi gives the Li13 cage [[[O-P(mu-NtBu)]2Li2]3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [O-P(mu-NtBu)]2(2-) dianion that is isoelectronic with ligands of the type [(RN)P(mu-NR)]2(2-). 相似文献
11.
Dodds F García F Kowenicki RA McPartlin M Steiner A Wright DS 《Chemical communications (Cambridge, England)》2005,(29):3733-3735
The reaction of [ClP(mu-NtBu)]2 with 1,5-diamino-naphthalene [1,5-(NH2)2C10H6] in Et3N-thf gives the trimeric macrocycle [{P(mu-NtBu)}2{1,5-(NH)2C10H6}]3(1); the X-ray structure of the toluene solvate 1.3toluene reveals a cone-shaped (calixarene-like) arrangement in which toluene guest molecules are trapped within the cavity. 相似文献
12.
13.
The Crystal Structure of Tetrakis(di-tert.-butylphosphino)diphosphane [(tBu)2P]2P? P[P(tBu)2]2 [(tBu)2P]2P? P[P(tBu)2]2 1 obtained at ?20°C from a solution of (tBu)2P? P=P(Br)tBu2 forms yellow crystals (regular hexagons). 1 crystallizes monoclinic in the space group C2/c with a = 2145.6pm, b = 1137pm, c = 1696.1pm, β = 110.075° and Z = 4 formula units in the elementary cell. Due to high steric load the bond angles at the tertiary P atoms with δ = 115.7° are significantly larger than those at the primary P atoms with δ = 108.6°. 相似文献
14.
Bezombes JP Hitchcock PB Lappert MF Nycz JE 《Dalton transactions (Cambridge, England : 2003)》2004,(4):499-501
Treatment of P(X)(X')Cl with KC8 gave the crystalline diphosphine [P(X)X']2 (1) which dissociated reversibly into the phosphinyl radical *P(X)X' (2), a plausible intermediate in the reaction of with [Cr(CO)6], [Co(NO)(CO)3] or P4, yielding [Cr[P(X)X']2(CO)3] (3), [Co[P(X)X'](CO)3] (4), or 1,4-P4[P(X)X']2 (5); the P(X)X' substituent is pyramidal at P in but planar in [X = N(SiMe3)2, X'= NPri2]. 相似文献
15.
《Journal of Coordination Chemistry》2012,65(11):2028-2033
The new cyclic phosph(V)azane ligand [(C6H5N)P(O)H]2 (2) is obtained from the reaction between PCl3 and PhNH2 in toluene followed by controlled hydrolysis of the product in an H2O–CHCl3 solution. Compound 2 is the first example of P(V) dimer [(µ-NC6H5)P(H)=O]2, a P2N2 ring with two P(O)H moieties. The reaction of 2 with ZnCl2 in a molar ratio of 1?:?1 in tetrahydrofuran yields the cyclophosph(V)azane complex Cl2Zn[(C6H5N)P(O)H]2 (3) in which Zn–O bonds form directly between a cyclic phosph(V)azane ligand and Zn(II). The products have been characterized by infrared, multinuclear (1H, 31P, 13C) NMR, mass spectrometry, and elemental analysis. 相似文献
16.
17.
H ? C Bond Cleavage in Ferrocene by Organylruthenium Complexes Cp*(Me3P)2RuCH2CMe3 ( 1 ) reacts at 85°C with ferrocene ( 2 ) by cleavage of one H? C bond in 2 to give CpFe[η5-C5H4Ru(PMe3)2Cp*] ( 3 ) (Cp = η5-C5H5; Cp* = η5-C5Me5) and neopentane. The ruthenium atom in 3 has a distorted tetrahedral geometry, the planar Cp ligands in the ferrocenyl fragment are eclipsed. Solutions of 3 in [D6]benzene or [D8]THF exhibit H? D exchange of the ferrocenyl protons. In the [D8]THF molecule only the α-deuterium atoms are exchanged. Reaction pathways for this exchange are discussed. 相似文献
18.
McArdle CP Van S Jennings MC Puddephatt RJ 《Journal of the American Chemical Society》2002,124(15):3959-3965
The design and synthesis of a new type of topologically chiral [2]catenane is reported. The compounds are formed easily by self-assembly on reaction of the oligomeric digold(I) diacetylide precursor complex [[4-BrC(6)H(4)CH(4-C(6)H(4)OCH(2)CCAu)(2)](n)] with diphosphine ligands. Reactions with the diphosphines PP = bis(diphenylphosphinophoshino)acetylene, trans-1,2-bis(diphenylphosphino)ethylene, bis(diphenylphosphino)ethane, and 1,1'-bis(diphenylphosphino)ferrocene yield simple ring complexes [4-BrC(6)H(4)CH(4-C(6)H(4)OCH(2)CCAu)(2)(mu-PP)] as the only products, since the spacer groups in the diphosphines are not long enough or are too bulky to allow catenane formation. Reaction with PP = bis(diphenylphosphino)propane or bis(diphenylphosphino)butane gave [2]catenane complexes [[4-BrC(6)H(4)CH(4-C(6)H(4)OCH(2)CCAu)(2)(mu-PP)](2)], whose structures are confirmed crystallographically. The macrocyclic ring compounds have C(s) symmetry but, as a result of the presence of the unsymmetrical "hinge group" 4-BrC(6)H(4)CH, the [2]catenanes have C(2) symmetry and so are topologically chiral. In favorable cases, the formation of the [2]catenane can be proved by NMR spectroscopy since catenane formation leads to nonequivalence of most ring atoms. The formation of the [2]catenanes was successfully predicted based on the conformation of the precursor bis(phenol), and it is argued that the methods used should be more generally applicable to the synthesis of functionally substituted supermolecules of interest for application in molecular devices. 相似文献
19.
[(tBu)2P]2P? P[P(tBu)2]2 from LiP[P(tBu)2]2 and 1,2-Dibromomethane. Pyrolysis of tBu2P? P?P(Br)tBu2 All products of the reaction of [tBu2P]2PLi 1 with 1,2-dibromoethane 2 were investigated. Already at ?70°C tBu2P? P?P(Br)tBu2 3 as main product and [tBu2P]2PBr 4 are formed. Only with an excess of 1 also [tBu2P]P? P[P(tBu)2]2 5 is obtained. Warming of a pure solution of 3 in toluene from ?70°C to ?30°C leads to 4 , and at 20°C tBu2PBr and the cyclophosphanes P4[P(tBu)2]4 and P3[P(tBu)2]3 are observed. 5 does not result from 3 , it's rather a byproduct from the reaction of 1 with 4 . Also the ylide 3 and 1 yields 5 . 相似文献