Arlan D. Norman

Tri-s-triazine derivatives. Part I. From trichloro-tri-s-triazine to graphitic C3N4 structuresPart II: Alkalicyamelurates M3[C6N7O3], M = Li, Na, K, Rb, Cs, manuscript in preparation.

The first detailed structural characterisation of a functionalised tri-s-triazine derivative, trichloro-tri-s-triazine, is reported, which is a promising starting material for numerous compounds including graphitic C3N4 phases. DFT calculations show that a C3N4 structure based on tri-s-triazine should exist and that it is ∼30 kJ mol−1 more stable than the previously reported C3N4 phase of lowest energy.

Metal-templated synthesis of a macrocyclic triphosphine-molybdenum complex, fac-(CO)/sub 3/Mo(PHC/sub 3/H/sub 6/)/sub 3/

This communication reports the first synthesis of a metal complex containing the (12)ane-P/sub 3/ triphosphine macrocycle (HPCH/sub 2/CH/sub 2/CH/sub 2/)/sub 3/. This reaction is an example of a reaction which takes advantage of a kinetic template effect. The reaction exemplifies the kinetic template effect since uncoordinated allylphosphine when treated with AIBN yields entirely different products. The reaction is clean, resulting in only slight molybdenum carbonyl complex degradation and no evidence for intramolecular ring closure to form coordinated phosphabutane rings or intermolecular P-H bond addition. The reaction is highly regiospecific; no Morkovnikov addition product has been detected. Studies of the generality of this metal-templated cyclization approach, derivatization of the hydridomacrocycles complexes, and displacement of the macrocyclic phosphine from the metal are in progress currently.

STRUCTURAL STUDIES OF N-N-BIS(DICHLOROPHOSPHINO) PHENYLAMINES

Abstract The structural characterization of PhN(PCl2)2 and m-MeC6H4N(PCl2)2 in solution by 31P NMR spectroscopy and of PhN(PCl2)2 in the solid by single crystal X-ray analysis is reported. PhN(PCl2)2 adopts a C2v conformation in the solid, in which the phosphorus lone pair electrons are eclipsed and both trans to the Ph group. The C2v conformation assignment for PhN(PCl2)2 and m-MeC6H4N(PCl2)2 is consistent with the low temperature 31P NMR spectral data. PhN(PCl2)2 crystallizes in space group P21, a=6.360(2) A, b=25.618(11) A, c=7.146(2) A, β=90.62(2) deg, Z=4, with two independent molecules per unit cell. The structure was solved and refined by direct methods to R=0.058 and Rw=0.078 for 671 independent reflections. Mean distances (A) and angles (deg) are: P-Cl, 2.036(13); P - N, 1.69(3);

Synthesis, spectroscopic characterization and x-ray studies of new complexes of organotin(IV) chlorides with N-alkylated 2-amino-1-cyclopentene-1-carbodithioic acids

The new complexes [Ph2SnCl(BuACDA)] (1), [Ph3Sn(BuACDA)] (2), [Bu2Sn(BuACDA)2] (3), [Ph2SnCl- (EtACDA)] (4), [Ph3Sn(EtACDA)] (5) and [Bu2Sn(EtACDA)2] (6) have been prepared from reactions between 2-N-butylamino-1-cyclopentene-1-carbodithioic acid (BuACDA) or 2-N-ethylamino-1-cyclopentene-1-carbodithioic acid (EtACDA) and Ph2SnCl2, Ph3SnCl or Bu2SnCl2. The 1H NMR, 119Sn NMR, UV-Vis and IR data and the elemental analyses support the structures of these organotin compounds. In all these complexes, the S–H proton has been removed and coordination takes place through the carbodithioate group. The 119Sn NMR data are consistent with the presence of five-coordinated tin(IV) in solution. Structures of 1 and 3 have also been confirmed by single crystal X-ray crystallography. The crystals of both are triclinic with space group . In the structure of 1, the tin environment is distorted trigonal bipyramidal with the Cl and one of the sulfur atoms in apical positions. In the structure of 3 the overall geometry at tin is highly distorted trans octahedral with the four S atoms on the equatorial plane. In both complexes, the ligand is asymmetrically chelated to the tin and there is an intramolecular hydrogen bond between the sulfur and the proton of the amine group.

CONVERSION OF ALLYLPHOSPHINE TO NOVEL DIPHOSPHINES: SYNTHESIS AND CHARACTERIZATION OF CH2=CHCH2P(H)(CH2)3PH2 AND P[(CH2)3]3P1

Abstract Irradiation (λ = 300–600 nm) of gaseous CH2=CHCH2PH2 in a hot-cold reactor yields the new diphosphine, CH2=CHCH2P(H)(CH2)3PH2(I). I results from the intermolecular head-to-tail addition of phosphine PH bonds to the C=C bonds of CH2=CHCH2PH2, in an anti-Markovnikov process. The AIBN-initiated radical reaction of CH2=CHCH2PH2 in benzene yields PH3 and the novel bicyclic diphosphine, P[(CH2)3]3P(II). Characterization of I and II, based on 31P, 1H, and 13C NMR and mass spectral data, is described.

The synthesis of (trimethylstannyl)phosphine: The observation of phosphorus—tin nuclear spin-spin coupling

Abstract (Trimethylstannyl)phosphine, (CH 3 ) 3 SnPH 2 , has been prepared in high yield by the reaction of LiAl(PH 2 ) 4 with (CH 3 ) 3 SnCl. The product has been characterized by elemental analysis, 1 H and 31 P NMR, IR, and mass spectral data. Reactions between (CH 3 ) 3 SnPH 2 and acidic reagents have been studied. The first measurement of 1 J (Sn P) has been made.

A new class of silicon-phosphorus heterocycles: 4-silaphosphorinanes

Abstract Radical reactions of Me3SiPH2 with Me2Si(CHCH2)2 or Si(CHCH2)4 yield the 4-silaphosphorinanes Me2Si(CH2CH2)2PSiMe3, (CH2CH)2Si(CH2CH2)2PSiMe3, or [Me3SiP(CH2CH2)2]2Si; methanolysis of these produces quantitatively the secondary phosphorinanes Me2Si(CH2CH2)2PH, (CH2CH)2Si(CH2CH2)2PH, or [HP(CH2CH2)2]2Si. Me2Si(CH2CH2)2PSiMe3 with O2/H2O yields the phosphinic acid Me2Si(CH2CH2)2P(O)OH. All compounds are characterized by spectral data; an X-ray crystal analysis confirms the structure of Me2Si(CH2CH2)2P(O)OH.

REDISTRIBUTION OF PRIMARY SILYL- AND GERMYLPHOSPHINES: SYNTHESIS OF TRISILYL- AND TRIGERMYLPHOSPHINES

Abstract Redistribution reactions of SiH3PH2, Si2H5PH2, SiH3PH2/Si2H5PH2, and GeH3PH2 promoted by BX3(X=F, Cl, Br), B2H6, and B5H9 as routes to the trisilyl- and trigermylphosphines (SiH3)3P, (Si2H5)3P, (SiH3)2PSi2H5, and (GeH3)3P have been examined. Reaction of the silyl- or germylphosphine borane complex (e.g. SiH3PH2·BF3) with the uncomplexed silyl- or germylphosphine (e.g. SiH3PH2) appears essential to the redistribution process. Trisilylphosphines and (GeH3)3P are best obtained in RPH2(R=SiH3, Si2H5)‒BF3 and GeH3PH2‒B5H9 reaction systems, respectively.

Synthesis and characterization of a primary amine-substituted bis(phosphino)amine metal complex cis-PhN[P(NHPh)2]2 Mo(CO)4

Die Titelverbindung (III) wird wie aufgezeigt auf drei Wegen aus (I), (IV) oder (V) erhalten und IR-, massen- sowie 1H- und 31P-NMR-spektroskopisch charakterisiert.

SILYLPHOSPHINE - ALKENE REACTION ROUTES TO ACYCLIC AND CYCLIC ORGANOPHOSPHINES

Abstract Radical reactions of Me3SiPH2, (Me3Si)2PH, Me2Si(PH2)2 and PH3 with selected alkenes have been examined as routes to new organo(silyl)phosphines. The Me3SiPH2/1,5-hexadiene reaction initiated by AIBN yields the phosphepane Me3SiP(CH2)6 (11a) and acyclic Me3SiP[(CH2)4CH=CH2]2 (12); the Me3SiPH2/1,3-butadiene reaction yields only acyclic butenyl phosphines Me3SiP(H)C4H7 (14a - C) and Me3SiP(C4H7)2 (15a - D). Reactions of Me3SiPH2 with P(CH=CH2)3 and MeSi(CH=CH2)3 yield the vinyl-substituted cis- and trans-phosphorinanes (CH2=CH)P(C2H4)2PSiMe3 (18a/18b) and Me(CH2=CH)Si(C2H4), PSiMe3 (20a/20b). (Me2Si)2PH/Me2Si(CH=CH2)2 reaction produces only the acyclic (CH2=CH)Me2SiC2H4P(SiMe3)2 (22) and Me2Si[C2H4P(SiMe3)2]2 (25). The Me2Si(PH2)2/1,4-pentadiene reaction yields phosphorinanyl derivatives Me2Si(PH2)[P(CH5] (27) and Me2Si[P(CH2)5]2 (28): no large-ring products form. The AIBN initiated reaction of CH2=CHCH2PH2 has been reinvestigated; the known bicyclic [(CH2)3]2P2 is obtained instead of the previous...