24103-44-4Relevant academic research and scientific papers
Mono-, Di-, and triborylphosphine analogues of triarylphosphines
Bailey, Jonathan A.,Ploeger, Marten,Pringle, Paul G.
, p. 7763 - 7769 (2014)
Diazaborinylphosphines based on the 1,8-diaminonaphthylboronamide heterocycle are prepared by a chlorosilane-elimination reaction, and their structural and bonding properties are compared to those of PPh3. The precursor chloroborane ClB{1,8-(NH)2C10H6} (I) is fully characterized including its crystal structure, which features intermolecular π-π stacking, B···N interactions, and N-H···Cl hydrogen bonding. Treatment of I with Ph 3-nP(SiMe3)n gave the corresponding Ph 3-nP(B{1,8-(NH)2C10H6}) n, {L1 (n = 1), L2 (n = 2), and L3 (n = 3)}. The crystal structures of L1-3 reveal an increase in the planarity at P as a function of n, and the steric bulk of the diazaborinyl substituent B{1,8-(NH)2C10H6} is similar to that of a phenyl. Nucleus-independent chemical shift calculations were carried out that suggest that the 14 π-electron diazaborinyl substituent can be described as aromatic overall, though the BN2-containing ring is slightly antiaromatic. The complexes cis-[Mo(L1-3) 2(CO)4] (1-3) are prepared from [Mo(nbd)(CO)4] (nbd = norbornadiene) and L1-3. From the position of the (CO) (A 1) band in the IR spectra of 1-3, it is deduced that the diazaborinyl substituent has a donating capacity similar to an alkyl group.
Indium(III) promoted oxidative P-P coupling of silylphosphines
Cartlidge, Ashleigh J.,Matthews, Peter D.
supporting information, (2022/01/28)
The reaction of indium(III) salts with Ph2PSiMe3 and PhP(SiMe3)2 gives rise to a one- and two-electron reductive P-P coupling respectively, with the formation of new P-P bonds resulting in the preparation of (Ph2P)2 and the cyclicoligophosphane compounds (PhP)4 and (PhP)6.
Phosphacycloalkyldiones: synthesis and coordinative behaviour of 6- And 7-member cyclic diketophosphanyls
Pearce, Kyle G.,Simenok, Vladimir,Crossley, Ian R.
, p. 5482 - 5492 (2020/05/16)
Glutaryl and adipoyl chlorides undergo facile condensation with the bis(silyl)phosphanes RP(SiMe3)2(R = Me,nBu,tBu, Ph, Mes) to afford exclusively the phosphacycloalkyldiones (CH2)n(C)2PR (n= 3,4). Characterised spectroscopically and, for R = Ph, Mes (n= 3) crystallographically, the macrocycles are conformationally fluxional in solution and appreciably moisture sensitive. Though seemingly resistant to chemical oxidation at phosphorus, coordination is readily achieved, as illustrated by isolation oftrans-[Pt(PEt3){P(Ph)(CO)2(CH2)3}Cl2] and a series of tungsten pentacarbonyl complexes, which are characterised crystallographically and by infrared and NMR spectroscopy. Together, these data suggest the macrocycles to be relatively weak σ-donors with no appreciable π-acceptor character.
Triphenylphosphaalkenes in Chemical Equilibria
D'Imperio, Nicolas,Arkhypchuk, Anna I.,Mai, Juri,Ott, Sascha
supporting information, p. 1562 - 1566 (2019/02/05)
Triphenylphosphaalkenes 1a–c were prepared in good to excellent yields in a modified phospha-Peterson reaction between PhP(Li)TMS and benzophenones with different para-substituents at the C-phenyl groups (a: R = H, b: R = O-octyl, c: R = F). Owing to the
Triarylalkenes from the site-selective reductive cross-coupling of benzophenones and aldehydes
Arkhypchuk, Anna I.,D'Imperio, Nicolas,Ott, Sascha
supporting information, p. 6030 - 6033 (2019/06/03)
PhP(Li)TMS converts benzophenones to phosphaalkenes which upon activation under oxidizing, basic conditions react with aromatic aldehydes under the formation of triarylalkenes. The one-pot reaction omits transition metals, proceeds at room temperature and precludes the formation of any homo-coupling products. Systematic substrate variations reveal reactivity patterns that are useful for the identification of ketone/aldehyde combinations that can be coupled in yields up to 80%.
Dithieno[3,2-c:2′,3′- e ]-2,7-diketophosphepin: A unique building block for multifunctional π-conjugated materials
He, Xiaoming,Borau-Garcia, Javier,Woo, Alva Y. Y.,Trudel, Simon,Baumgartner, Thomas
supporting information, p. 1137 - 1147 (2013/04/10)
A series of conjugated materials based on the new dithieno[3,2-c:2′, 3′-e]-2,7-diketophosphepin (DTDKP) building block have been studied for the first time. Theoretical calculations predict DTDKP to be a better electron acceptor than the well-known dithienophosphole and the nitrogen analogue, bithiopheneimide. Cyclic voltammetry studies revealed two reduction processes that support their promising electron-acceptor properties, and modification of the P center with O or gold(I) further reduced the LUMO energy to ca. -3.6 eV. Expansion of the DTDKP core with various aromatic moieties has been realized using the Huisgen alkynyl click reaction, resulting in altered optical and electrochemical properties with compounds showing a high-energy absorption band at ca. 270-290 nm and a low-energy band at ca. 390-460 nm. The acceptor character of the DTDKP core was demonstrated by a red shift following the electron-donating strength of the appended aromatic moiety. Intriguing white-light emission from just a single species with the CIE coordinates of (0.33, 0.34) was observed for some of the extended species as the result of an unexpected dual-emission behavior. The high-energy emission in the blue-to-green region and the low-energy emission in the orange-to-red region are attributed to a π* → π transition of the DTDKP core and charge transfer from the triazole moiety to DTDKP, respectively. Apart from tuning of the molecular properties, this novel building block has also been applied in a self-assembled organogel, which exhibited pronounced luminescence. Scanning electron microscopy confirmed that the gel self-assembled by forming a network of entangled 1D fibrous structures on the micrometer scale.
