Crystal structure analysis of (N-methyl piperazino) (phenyl) (dicyclohexylamino) phosphiniminocyclotrithiazene
01 Jan 2005-Journal of Chemical Crystallography (Kluwer Academic Publishers-Plenum Publishers)-Vol. 35, Iss: 1, pp 27-34
TL;DR: In this paper, the tricoordinated sulfur atom (S1) in the cyclotrithiazene was shown to be highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or −1.0) for the cyclic and acyclic substituents in the (R)(C6H5)2]P{-S3N3 series.
Abstract: The title compound (NC4H8NCH3)(C6H5)[N(C6H11)2]P{—N–S3N3 crystallizes in the triclinic crystal system with unit cell dimensions: a = 9.7572(2), b = 10.6845(1), c = 16.9381(3) A, α = 71.75(1)∘, β = 80.65(2)∘, γ = 65.93(1)∘, and Z = 2. The tricoordinated sulfur atom (S1) in the cyclotrithiazene deviates from the mean plane of the other five atoms by 0.716(6) A, which is the highest among the known phosphiniminocyclotrithiazene structures. In the exocyclic P{—N4–S1 moiety, the two bond distances are short: 1.585(6) and 1.527(6) A; but the bond angle is large 135.3(4)∘. The S1 displacement is highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or −1.0) for the cyclic and acyclic substituents (R) in the (R)(C6H5)[N(C6H11)2]P{—N–S3N3 series. On the other hand, the S1–N4 bond distances are negatively correlated (R = −0.94) with the P{—N4–S1 bond angle in the above series.
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TL;DR: The chemistry of simple acyclic aminophosphines (synthesis, characterization, reactivity and applications) is covered and particular focus is given to their ability to form chalcogenides along with their role played as ligands in coordination chemistry and as synthons in inorganic heterocyclic chemistry as mentioned in this paper.
Abstract: In recent years, research in organophosphorus chemistry has mainly focused in designing newer and better phosphorus ligands for synthesizing novel metal complexes with improved catalytic activities. Aminophosphines [tricoordinate phosphorus(III)–nitrogen systems] are considered as versatile compounds owing to the presence of nitrogen centres which, in principle, can influence additional reactivity features. They are quite sensitive to air and moisture due to the presence of polar PN bond(s). In spite of this, research in aminophosphine chemistry is gaining momentum day-by-day and this is due mainly to one reason: their rich behaviour as ligands in metal complex chemistry and subsequently in catalysis. Their role as synthons in inorganic heterocyclic chemistry has also helped produce new types of heterocycles. In this paper, the chemistry of simple acyclic aminophosphines (synthesis, characterization, reactivity and applications) is covered and particular focus is given to their ability to form chalcogenides along with their role played as ligands in coordination chemistry and as synthons in inorganic heterocyclic chemistry. Copyright © 2009 John Wiley & Sons, Ltd.
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TL;DR: An electron rich hybrid aminophosphine, (diisopropylamino)(morpholino) (phenyl)phosphine L, was synthesized in good yield by step-wise aminolysis reactions with dichloro(phenyl)-phosphines and structurally characterized as mentioned in this paper.
Abstract: An electron rich “hybrid” asymmetric aminophosphine, (diisopropylamino)(morpholino) (phenyl)phosphine, L, was synthesized in good yield by step‐wise aminolysis reactions with dichloro(phenyl)phosphine and structurally characterized. The complex, CuCl(L) was readily isolated from both 1∶1 and 1∶2 reactions of L with CuCl. Single crystal X‐ray structures of L and two copper complexes, [CuCl(L) · CH3CN]2 (1) and [CuCl(L) · CH2Cl2]2 (2) have been determined. X‐ray structures reveal pyramidal nature of phosphorus and near planar geometry of nitrogen of the phosphine ligand and the dimeric nature of the complexes with tricoordinate copper(I) centers. The asymmetric phosphine crystallizes in monoclinic system with space group P21/c and unit cell dimensions as a=17.219(1) A, b=13.469(1) A, c=7.395(5) A, α=90.00°, β=93.11(1)°, γ=90.00°. Both acetonitrile (1) and dichloromethane (2) solvates crystallize in triclinic system with space group Pī. The unit cell dimensions of (1) are a=10.143(2) A, b=13.681(3) A, c=16.6...
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TL;DR: Phosphinazines with the PNNC framework comprise a novel class of compounds owing to the presence of both phosphinimino and ketimino moieties as discussed by the authors, and there are very few known examples in this set.
Abstract: Phosphinazines with “PNNC” framework comprise a novel class of compounds owing to the presence of both phosphinimino and ketimino moieties. There are very few known examples in this set and their u...
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TL;DR: In this article, the extent of participation of d orbitals in molecular bonding was investigated and available evidence made it possible to speculate with more certainty on the extent participation of orbitals.
Abstract: Available evidence now makes it possible to speculate with more certainty on the extent of participation of d orbitals in molecular bonding.
89 citations
TL;DR: The deformation electron density in sulfamic acid (H3NSO3) has been determined by a combined X-ray and neutron diffraction study at 78 K as discussed by the authors.
Abstract: The deformation electron density in sulfamic acid (H3NSO3) has been determined by a combined X-ray and neutron diffraction study at 78 K. X-N maps show strong bond populations in all bonds. The nature of the S--N and S O bonds is found to be similar to bonds between first-row atoms. The O atoms show single, fairly broad lone-pair peaks and are shifted towards the lone pairs in comparison with the neutron parameters. This shift disappears when only X-ray reflections with sin 0//1, > 0.85 A -1 are considered. A population analysis shows a net charge of +0.7 to +1.0 e on the S atom, -0 .3 to -0 .5 e on the O atoms and + 0.12 e on the H atoms, while the N atom is close to neutral.
65 citations
TL;DR: In this paper, a ring system containing Ferrocenyl Substituents is synthesized starting from FcPCl2 (1, FcPH2 (2), FcAsCl2(3) and Fe(C5H4A6H2)2 (4), which contains an eight-membered As2S2N4 ring.
Abstract: Ausgehend von FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) und Fe(C5H4AsCl2)2 (4) werden drei-, vier-, funf- und achtgliedrige Heterocyclen mit Ferrocenyl-Substitutenten synthetisiert (Fc = Ferrocenyl). Durch Umsetzung von 1 mit 2 in Gegenwart von DBU entsteht (FcP)n, das mit (Ph3P)2Pt(C2H4) zu (7) reagiert. Der analoge As2Pt-Ring 9 ist uber (FcAs)3 (8) in guter Ausbeute zuganglich. Die Reduktion von 1 mit LiAlH4 liefert (FcP)4 (10). Ein funfgliedriger Arsen-Schwefel-Heterocyclus, Fc2As2S3 (12), entsteht durch Umsetzung von FcAs=P(2,4,6-tBu3C6H2) (11) mit Schwefel. FcAsCl2 (3) reagiert mit Me3SiNSNSiMe3 zu FcAs(NSN)2AsFc (13), das einen achtgliedrigen As2S2N4-Ring enthalt. Dessen Komplexierung mit (Norbornadien)M(CO)4 fuhrt zu den Tetracarbonyl-Komplexen [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). Ein Arsenuberbrucktes Ferrocenophan 16 kann bei der Reaktion von Fe(C5H4Li)2 × TMEDA mit AsCl3 isoliert werden. Auch die Umsetzung von 4 mit Me3SiNSNSiMe3 liefert ein kondensiertes Ferrocenophan-Derivat der Zusammensetzung (C5H4)2FeAs2N6S4 (17). Die Molekulstrukturen von 13 und 17 wurden rontgenographisch bestimmt.
Inorganic Ring System Containing Ferrocenyl Substituents
Three-, four-, five-, and eight-membered heterocycles are synthesized starting from FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) and Fe(C5H4AsCl2)2 (4) (Fc = Ferrocenyl). Treatment of 1 with 2 in the presence of DBU yields (FcP)n, which reacts with (Ph3P)2Pt(C2H4) to give (7). The corresponding As2Pt ring system 9 is available in high yield via (FcAs)3 (8). The reduction of 1 with LiAlH4 yields (FcP)4 (10). A five-membered arsenic sulfur heterocycle, Fc2As2S3 (12), is formed in the reaction of FcAs=P(2,4,6-tBu3C6H2) (11) with sulfur. FcAsCl2 (3) reacts with Me3SiNSNSiMe3 to give FcAs(NSN)2AsFc (13), which contains an eight-membered As2S2N4 ring. Its complexation with (norbornadiene)M(CO)4 leads to the tetracarbonyl complexes [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). An arsenic-bridged ferrocenophane 16 can be isolated from the reaction of Fe(C5H4Li)2 x TMEDA with AsCl3. The reaction of 4 with Me3SiNSNSiMe3 also produces a condensed ferrocenophane derivative, (C5H4)2FeAs2N6S4 (17). The molecular structures of 13 and 17 have been determined by X-ray diffraction.
56 citations