Preparation and ligating properties of the first example of a 1,2,4-triphosphole, P3C2But2R [R = CH(SiMe3)2]: crystal and molecular structures of P3C2But2CH(SiMe3)2, trans-[PtCl2(PEt3){P3But2CH(SiMe3)2}]and[Fe2(CO)6{µ-P3C2But2CH(sime<su

Caliman, Vinicius; Hitchcock, Peter B.; Nixon, John F.

doi:10.1039/c39950001661

Cited by 46 publications

(32 citation statements)

References 6 publications

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“…doublets at δ 111.2, 179.2 and 243.7 easily identify compound 1, which has been completely characterized. 10 The proposed structure for compound 5 ( Figure 2) is based on this spectrum which shows the two phosphorus resonances at δ 106.8 and 181.5, which are typical for sp 3 and sp 2 hybridized phosphorus, respectively. Each signal appears as a doublet with a coupling constant 1 J pp = 523.6 Hz, typical for a direct P-P bond.…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of the first triphosphole, 1-[bis(trimethylsilyl)methyl]-3-5-di-tert-butyl-1,2,4-triphosphole (1) (Figure 1) was reported 10 by one of us in 1995. This molecule showed some planarity, with the sum of bond angles around the sp 3 phosphorus atom equal to 342°, which is considerably greater than the analogous mono and diphospholes (302 and 320°, respectively).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms

Rocha

Duarte

Almeida

et al. 2002

J. Braz. Chem. Soc.

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A síntese de dois novos arsadifosfóis de fórmula (AsP 2 C 2 Bu t 2 )CH(SiMe 3 ) 2 , a partir dos anéis aniônicos 4-arsa-1,2-difosfaciclopentadienil e 2-arsa-1,4-difosfaciclopentadienil é reportada, junto com suas caracterizações utilizando RMN de 31 P. Cálculos ab initio no nível MP2/6-31G(d) de teoria foram realizados para se investigar as barreiras de inversão piramidal, estabilidade relativa e o caráter aromático de todos os possíveis isômeros dos arsadifosfóis, em fase gasosa. A distribuição termodinâmica dos isômeros está em completo acordo com os resultados experimentais. O caráter de aromaticidade obtido para os três isômeros contendo um fósforo sp 3 é maior quando comparado com o 1,2,4-trifosfol, sintetizado previamente. Os efeitos dos grupos substituintes volumosos sobre a aromaticidade e as barreiras de inversão piramidal são também discutidos.The synthesis of two new arsadiphospholes of formula (AsP 2 C 2 Bu t 2 )CH(SiMe 3 ) 2 , from 4-arsa-1,2-diphosphacyclopentadienyl and 2-arsa-1,4-diphosphacyclopentadienyl ring anions are reported together with their characterization by 31 P NMR. Ab initio calculations at the MP2/6-31G(d) level of theory were carried out to investigate the energy barrier for pyramidal inversion about the pyramidal P and As atoms, relative stability and aromaticity character of all possible isomers in the gas phase. The thermodynamic isomers distribution is in agreement with the experimental results. The inversion barrier at the sp 3 phosphorus compared to the inversion barrier found for the arsenic atom is low. This fact is directly related with the aromaticity of the rings and shows the preference of the side group for the phosphorus atom, which leads to a more aromatic ring structure. The aromaticity character found for three isomers containing a sp 3 -phosphorus is greater if compared with that of 1,2,4-triphosphole synthesized previously. The effects of bulky R substituents on the aromaticity and on the energy barrier for pyramidal inversion are also discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms

Rocha

Duarte

Almeida

et al. 2002

J. Braz. Chem. Soc.

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“…[1]. Of special interest is the greatly enhanced aromatic behavior of the 1,2,4-triphosphole ring system (1) compared with phospholes themselves, and in its complexes with both [M(CO) 3 ] fragments (M ‫ס‬ Cr, Mo, W) and with [Ru(0) (cyclooctadiene)], it is also a 6e donor, but now the ring is essentially planar [2,3].…”

Section: Introductionmentioning

confidence: 98%

“…Of special interest is the greatly enhanced aromatic behavior of the 1,2,4-triphosphole ring system (1) compared with phospholes themselves, and in its complexes with both [M(CO) 3 ] fragments (M ‫ס‬ Cr, Mo, W) and with [Ru(0) (cyclooctadiene)], it is also a 6e donor, but now the ring is essentially planar [2,3]. In a preliminary report [1], we also described the ligating behavior of the 1,2,4-triphosphole as a 2e donor in trans-[PtCl 2 (PEt 3 ){P 3 C 2 CH(SiMe 3 ) 2 }] (2). Here we ret Bu 2 port in full on this complex and its further unexpected reaction to ligate a second platinum(II) fragment, in which the ring is acting as a 4e donor.…”

Section: Introductionmentioning

confidence: 98%

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Triphospholes as2e and4e donors: Synthesis and structural characterization of the 1,2,4-triphosphole complexes ?1-trans-[PtCl2(PEt3)(P3C2But2CH(SiMe3)2] and ?1-?1-trans-[PtCl2(PEt3)2}2(?-P3C2But2CH(SiMe3)2]

1998

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Zur Reaktion vontert-Butyl-phosphaalkin mit Molybdänkomplexen

Scheer

Krug

1998

Z. anorg. allg. Chem.

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Die Umsetzung von tBuC≡P mit [(CH3CN)3Mo(CO)3] führt zum Zweikernkomplex [Mo(CO)4〈Mo(CO)2(η4‐P3CtBu){η4‐P2(CtBu)2}〉] 1 sowie den Carbinkomplexen [Mo(CO)4〈{P3(CtBu)2}{Mo(CO)2(CtBu)}{η3‐P2(CtBu)2}〉] 2 und [Mo(CtBu){η4‐P2(CtBu)2(CO)}{η5‐P3(CtBu)2}] 3 als isolierte Produkte. Alle Verbindungen wurden durch die Kristallstrukturanalyse, mittels NMR‐ und IR‐Spektroskopie sowie massenspektrometrisch strukturell charakterisiert. Der Zweikernkomplex 1 hat einen 1,3‐Diphosphacyclobutadienylring und einen 1,2,4‐Triphosphacyclobutadienylligand. In 2 sind ein 1,3‐Diphosphacyclobutadienylring und ein σ‐gebundener 1,2,4‐Triphospholylligand an zwei Mo‐Komplexzentren gebunden. Das Charakteristikum von 3 ist neben einem π‐gebundenen 1,2,4‐Triphospholyl‐ ein 3,4‐Diphosphacyclopentadienon‐Ligand, der sich durch CO‐Einschub während der Cyclodimerisierung zweier Phosphaalkine gebildet haben sollte.

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Preparation and ligating properties of the first example of a 1,2,4-triphosphole, P₃C₂Bu^t₂R [R = CH(SiMe₃)₂]: crystal and molecular structures of P₃C₂Bu^t₂CH(SiMe₃)₂, trans-[PtCl₂(PEt₃){P₃Bu^t₂CH(SiMe₃)₂}]and[Fe₂(CO)₆{µ-P₃C₂Bu^t₂CH(sime

Cited by 46 publications

References 6 publications

Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms

Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms

Triphospholes as2e and4e donors: Synthesis and structural characterization of the 1,2,4-triphosphole complexes ?1-trans-[PtCl2(PEt3)(P3C2But2CH(SiMe3)2] and ?1-?1-trans-[PtCl2(PEt3)2}2(?-P3C2But2CH(SiMe3)2]

Zur Reaktion vontert-Butyl-phosphaalkin mit Molybdänkomplexen

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