Showing papers by "John F. Nixon published in 1998"
Book•
25 Feb 1998
TL;DR: The Phosphorus-Carbon Analogy: Phospha-organic Chemistry as mentioned in this paper The Phosphinidenes (R-P) and Terminal Phphinidene Complexes [RP=M].
Abstract: The Phosphorus-Carbon Analogy: Phospha-organic Chemistry. Phosphinidenes (R-P). Terminal Phosphinidene Complexes [R-P=M]. Phosphaalkynes (RC=P). Phosphaalkenes, R1R2C=PR3. Phosphapolyenes. Diphosphenes (RP=PR). Phosphorus-Carbon Heterocyclic Chemistry. PI-Coordination Complexes. What Future for Phosphaorganic Chemistry? Index.
247 citations
TL;DR: The first isolable example of a molecular scandium(II) complex, the dark purple scandocene [Sc(η5-P2C3But3)] 1, has been isolated from the cocondensation of Scandium vapour with tert-butylphosphaalkyne, ButCP at 77 K as discussed by the authors.
55 citations
TL;DR: The Bird aromaticity index for 1 shows that it has the most pronounced aromatic character of all known phospholes.
Abstract: The sterically demanding groups on the tricoordinate phosphorus atom, the π-electron acceptors substituted on the ring, and the dicoordinate phosphorus atoms within the ring are the most significant factors contributing to the planarity and aromaticity of the 1,2,4-triphosphole ring in 1. The Bird aromaticity index for 1 shows that it has the most pronounced aromatic character of all known phospholes.
52 citations
TL;DR: In this article, a single crystal structural study of 2b showed that a shortening of the PC triple bond from 1.542(2) to 1.512(5) was achieved upon η1 co-ordination of the phosphaalkyne, which represents the shortest P-C bond so far reported.
Abstract: Treatment of trans-[FeH(Cl)(dppe)2] 1 (dppe = Ph2PCH2CH2PPh2) in thf with PCBut, in the presence of Tl[BF4], gave the η1-co-ordinated phosphaalkyne complex trans-[FeH(η1-PCBut)(dppe)2][BF4] 2a which forms trans-[FeH(η1-PCBut)(dppe)2][BPh4] 2b on reaction with Na[BPh4] or, upon reaction with HBF4 in CH2Cl2, converts into the η1-fluorophosphaalkene and the difluorophosphine complexes trans-[FeH(η1-PFCHBut)(dppe)2]A (A = BF4 3a or FeCl2F2 3b) and trans-[FeH(PF2CH2But)(dppe)2][BF4] 4, respectively. The phosphine complex trans-[FeH(PH3)(dppe)2][BF4] 5a was also formed in a reaction of 1 with PCBut in the presence of Tl[BF4] and [NH4][BF4] and converts into trans-[FeH(PH3)(dppe)2][BPh4] 5b upon treatment with Na[BPh4]. A single crystal structural study of 2b showed that a shortening of the PC triple bond from 1.542(2) to 1.512(5) A results upon η1 co-ordination of the phosphaalkyne, which represents the shortest P–C bond so far reported. The electrochemical PL ligand parameter has been estimated for η1-PCBut and its net electron donor/acceptor ability is compared with those of related unsaturated ligands.
22 citations
TL;DR: In this article, a reacao of [Ir4(m-CO)(CO)7{m4-h3-Ph2PC(H)C(Ph)PCBut} (m-PPh2)2] with PoCBut in CH2Cl2 a 35 °C por 4 h leva a formacao do composto inedito, which contem a cadeia 2-fosfabutadienilfosfina.
Abstract: A reacao de [Ir4(m-H)(CO)9(Ph2PCoCPh)(m-PPh2)] 1 com PoCBut em CH2Cl2 a 35 °C por 4 h leva a formacao do composto inedito [Ir4(m-CO)(CO)7{m4-h3-Ph2PC(H)C(Ph)PCBut}(m-PPh2)] 2, que contem a cadeia 2-fosfabutadienilfosfina. O composto 2 forma-se tambem quando [Ir4(CO)10(Ph2PCoCPh)(PPh2H)] 3 e aquecido na presenca de PoCBut, em thf, a 40 °C, por 48 h. Essas duas reacoes tambem produzem pequenas quantidades de [Ir4(m-CO)(CO)7(m3-h2-HCCPh)(m-PPh2)2] 4, porque as velocidades das transformacoes de 1 e de 3 em 4 e das reacoes desses compostos com PoCBut sao semelhantes. O composto 2 foi caracterizado por dados analiticos e espectroscopicos, espectrometria de massas usando fonte de FAB e experimentos de RMN de 1H, 31P, 13C, 2D 31P-1H HETCOR, diferenca de nOe e DEPT que levaram a sua formulacao e estabeleceram que havia ocorrido o acoplamento entre o ligante Ph2PCoCPh e o PoCBut e a migracao do hidreto para o Ca do Ph2PCoCPh. Entretanto, esses dados nao permitiram decidir se a clivagem da ligacao P-Csp do Ph2PCoCPh havia ocorrido e nem definir o modo de interacao da cadeia organofosforada. A estrutura molecular do composto 2, determinada por uma analise de difracao de raios-X, mostrou que o cluster exibe um arranjo metalico na forma de uma borboleta e que a cadeia organofosforada, corretamente formulada por dados espectroscopicos, interage com o poliedro metalico atraves de quatro ligacoes s.
11 citations
Journal Article•
TL;DR: In this article, room temperature electrocyclisation of the 1,2,4-triphosphole P3C2But2CH(SiMe3)2 affords the new 1,3,5-tri-phosphabicyclo[2.1]pent-2-ene which undergoes a very rapid [1,3]-phosphorus migration which can be stopped by coordination of [W(CO)5]; the two isomeric phosphorus compounds react differently with [PtCl2(PEt3)]2, the latter via an
11 citations
11 citations
TL;DR: In this paper, the reaction of 2,2-dimethylpropylidynephosphine with the cluster [Os3(CO)10(µ3-η1:η2: η1-C2Me] results in P-C bond cleavage and an insertion of the precoordinated but-2-yne ligand into the phosphorus carbon triple bond of the incoming phosphaalkyne with formation of a novel bridging C3P-moiety in the structurally characterised complex.
8 citations
TL;DR: In this paper, the first examples of clusters containing a phosphido fragment arising from hydrometalation and cleavage of the P−C triple bond of the phosphaalkyne were presented.
7 citations
TL;DR: The first η1-complexes of 1,2,4-triphospholes were reported in 1998, in which the ring acts as a 2e and a 4e donor as discussed by the authors.
Abstract: The first examples of η1-complexes of 1,2,4-triphospholes are reported in which the ring acts as a 2e and a 4e donor. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:1–8, 1998
5 citations
TL;DR: The trisulphido complex [PPh4][W(η5-(C5Me5)(S)3] as discussed by the authors reacts with the phospha-alkyne ButCP and O2 to afford the dimeric complex [S2PCtBu]2.