Synthesis, Spectroscopic Characterization and Crystal Structure of a New Acetyl phosphorylamidate P(O)[NHC(O)C6H4(4-NO2)][N(CH(CH3)2)(CH2C6H5)]2

Different orientations of P(O) versus C(O) in P(O)NHC(O) skeleton have been discussed in two new phosphorus(V)-nitrogen compounds with formula XP(O)Y and XP(O)Z 2 where X = NHC(O)C 6 H 4 (4-F) and Y = NHCH 2 C(CH 3 ) 2 CH 2 NH (1), Z = NHC 6 H 4 (4-CH 3 ) (2). Compound 1 is the first example of an aliphatic diazaphosphorinane with a gauche orientation which has been studied by X-ray crystallography; the P=O bond is in the equatorial position of the ring. Both compounds show n J(F,C) and m J(F,H) coupling constants (n = 1, 2, 3 and 4; m = 3 and 4) and 3 J(P,C) [ 2 J(P,C). Quantum chemical calculations were performed with HF and Density Functional Theory (DFT) methods using 6-31?G(d,p) basis set. A tentative assignment of the observed vibrational bands for these molecules is discussed. Compound 1 shows a deshielded C atom of the carbonyl moiety (in 13 C NMR spectrum) relative to that of 2, which is supported by IR spectroscopy in which the considerably lower C=O frequency is observed for 1. Comparing the X-ray crystallography and IR spectra of 1 and 2 shows that the acyclic compound 2, containing P=O and C=O bonds in an anti position, are involving in a stronger N-HÁÁÁO=P hydrogen bond in crystal network. This leads to a weaker P=O and N C(O)NHP(O) -H bonds and stronger NÁÁÁO interaction. The N amide -H is involved in an intramolecular N-HÁÁÁO hydrogen bond.

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“…Infrared (IR) spectra were recorded on a Buck 500 scientific spectrometer using KBr disc. 4-F-C 6 [7].…”

Section: Methodsmentioning

confidence: 99%

“…The anti orientation is preferred for the C=O versus P=O unit [6,7]. Some researchers have employed the anionic form [P(O)NC(O)] -to obtain compounds with a non-anti orientation [8] and better donority properties [9].…”

Section: Introductionmentioning

confidence: 99%

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

et al. 2010

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“…Following the previous works about carbacylamidophosphates with a C(═O)NHP(═O) skeleton such as P(O) (Pourayoubi & Sabbaghi, 2009) (Sabbaghi et al, 2010), here, we report the synthesis and crystal structure of title compound, P(O)…”

Section: S1 Commentmentioning

confidence: 98%

N,N′-Dibenzyl-N′′-(2,6-difluorobenzoyl)-N,N′-dimethylphosphoric triamide

et al. 2010

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The phosphoryl and carbonyl groups in the title compound, C23H24F2N3O2P, are anti to each other. The P atom is in a tetrahedral coordination environment and the environment of each N atom is essentially planar, the average bond angles at the two N atoms being 119.9 and 119.1°. The H atom of the C(=O)NHP(=O) group is involved in an intermolecular –P=O⋯H–N– hydrogen bond, forming centrosymmetric dimers.

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“…For a polyoxometalate-based inorganic-organic compound containing a phosphoryl ligand, see: Niu et al (1996). For phosphoric triamide compounds having a C( O)NHP( O) skeleton, see: Pourayoubi & Sabbaghi (2009) and references cited therein. For bond lengths in related structures, see: Sabbaghi et al (2010).…”

Section: Related Literaturementioning

confidence: 99%

“…The phosphoryl is a better H-acceptor relative to the carbonyl counterpart (Pourayoubi & Sabbaghi, 2009); so, the hydrogen atom of the C(═ O)NHP(═ O) group is involved in an intermolecular -P═O•••H-N-hydrogen bond (see Table 2) to form a centrosymmetric dimeric aggregate [graph set: R 2 2 (8) (Etter et al, 1990;Bernstein et al, 1995)…”

Section: Support Of This Investigation By Islamic Azad University-normentioning

confidence: 99%

N,N′-Dibenzyl-N′′-(2-chloro-2,2-difluoroacetyl)-N,N′-dimethylphosphoric triamide

2011

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Synthesis, Spectroscopic Characterization and Crystal Structure of a New Acetyl phosphorylamidate P(O)[NHC(O)C6H4(4-NO2)][N(CH(CH3)2)(CH2C6H5)]2

Cited by 11 publications

References 18 publications

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

N,N′-Dibenzyl-N′′-(2,6-difluorobenzoyl)-N,N′-dimethylphosphoric triamide

N,N′-Dibenzyl-N′′-(2-chloro-2,2-difluoroacetyl)-N,N′-dimethylphosphoric triamide

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