Jean-François Labarre

Extended CNDO/2 studies of the isoelectronic series AM(CO)3 (AM η6-C6H6Cr,η5-C5H5Mn,η4-C4H4Fe,η3-C3H5Co,η2-C2H4Ni) and of (η6-C6H6)2Cr

Abstract The electronic structure of isoelectronic AM(C0)3 (AM  η6-C6H6Cr,η5-C5-H5Mn,η4-C4H44Fe,η3-C3H5Co,η2-C2H4Ni) and of (η6-C6H6)2Cr is investigated within an extended CNDO/2 formalism using both experimental and standard geometries. The computed trends for bond strengths and stretching frequencies (as measured by Wiberg indices or bicentric energy terms) and for reactivity (charge distributions) correlate with the experimental ones. For chromium complexes, the extended CNDO/2 results seem more reasonable, for example the charge and the orbital populations on chromium, than are the ab initio single > results. A general agreement is observed between CNDO/2 and SCCC electronic structures.

Crystal and molecular structure of the two MACRO-ANSA and MACRO-SPIRO isomeric cyclotriphosphazenes N3P3Cl4 [HN(CH2)3O(CH2)4O(CH2)3NH]

Abstract Reaction of N 3 P 3 Cl 6 with 4,9-dioxadodecane-1,12-diamine (coded as 3O4O3) proceeds cleanly to yield two isomeric cyclotriphosphazenic species, namely MACRO-ANSA (3O4O3) and MACRO-SPIRO (3O4O3), depending on experimental conditions. These two chemicals crystallize in monoclinic and orthorhombic systems, respectively. MACRO-ANSA (3O4O3): P 2 1 / n , a =15.405(7), b =8.728(2), c =15.685(5)A, β=98.10(3)°, V =2088 A 3 , Z =4, D X =1.52(3) Mg m −3 , R =0.077 for 1743 unique observed reflections and 247 variable parameters. MACRO-SPIRO (3O4O3): P 2 1 2 1 , a =12.638(4), b =17.364(9), c =19.334(14) A, V =4242A 3 , Z =8, D X =1.50(5) Mg m −3 , R =0.046 for 1395 unique observed reflections and 441 variable parameters. The structures of these two isomers exhibit a spatial arrangement N 3 P 3 Cl 4 with [HN(CH 2 ) 3 O(CH 2 ) 4 O(CH 2 ) 3 NH] as a 17-membered arch onto two P atoms of the N 3 P 3 ring for the MACRO-ANSA derivative and as a 15-membered loop on one P atom of the N 3 P 3 ring for the MACRO-SPIRO compound.

An answer to the spiro versus ANSA dilemma in cyclophosphazenes: Part XII. The first MEGA-SPIRO and MEGA-ANSA species from trioxodiamines☆

Abstract Aminolysis of N 3 P 3 Cl 6 by trioxodiamines in suitable conditions yields two kinds of cyclophosphazenic MEGA-ANSA and MEGA-SPIRO species which constitute new macrocyclic ligands.

Crystal and molecular structure of a new allotropic variety of the mega-spiro cyclophosphazene from diethylene glycol bis-(3-aminopropyl)-ether, N3P3Cl4[HN(CH2)3O(CH2)2O(CH2)2O(CH2)3 NH)]

Abstract Reaction of N 3 P 3 Cl 6 with diethylene glycol bis-(3-aminopropyl)-ether (coded as 3O2O2O3) using a toluene/Na 2 CO 3 interface process yields cleanly the MEGA-SPIRO (3O2O2O3) species, the crystal and molecular structure of which was recently reported (allotropic variety A, orthorhombic, Pca 2 1 , Z =4). The same reaction, when performed in THF, leads to the MEGA-ANSA (3O2O2O3) isomer as the very major product, traces of MEGA-SPIRO (3O2O2O3) being separated by skillful SiO 2 column chromatography. This chemical crystallizes in the monoclinic system, C 2/ c, a =10.95(9), b =23.26(4), c =17.12(6) A, β=94.1(1)°, V =4350 A 3 , Z =8, D X =1.51(2) Mg m −3 , R =0.068 for 2188 unique observed reflections and 226 variable parameters. As expected the structure exhibits a spatial arrangement N 3 P 3 Cl 4 with (HN(CH 2 ) 3 O(CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 3 NH) as a 16-membered loop on one phosphorus atom of the N 3 P 3 ring (as in the allotropic variety A) but the conformation of this loop is different from the one in A. Thus, one may conclude that reaction of N 3 P 3 Cl 6 with diethylene glycol bis-(3-aminopropyl)-ether in THF yields a second allotropic variety B of the MEGA-SPIRO (3O2O2O3) as a by-product.

An answer to the spiro versus ansa dilemma in cyclophosphazenes Part XIV. The first MACRO-BINO and MEGA-BINO species from oxodiamines☆

Abstract Aminolysis of N 3 P 3 Cl 6 by oxodiamines in ethyl ether-Na 2 CO 3 saturated water (interface process) and in (2:1) stoichiometric conditions leads to MACRO-BINO and MEGA-BINO species which are starting materials for further syntheses of cyclophosphazenic crown ethers and cryptands.

An anwser to the sprio versus ansa dilemma in cylophosphazenes Part XV. The first MACRO-diBINO and MEGA-diBINO non-geminal species from oxodiamines

Abstract Aminolysis of N 3 P 3 Cl 6 by oxodiamines in ethyl ether-Na 2 CO 3 saturated water (interface process) [(1:1) stoichiometric conditions] or in 2-propanol [(1:2) stoichiometric conditions] leads stereoselectively and/or stereospecifically to MACRO-diBINO and MEGA-diBINO species which constitute a new class of macrocylic crown ethers.

Crystal and molecular structure of the megaspiro cyclophosphazenic species from diethylene glycol bis-(3-aminopropyl)-ether, N3P3Cl4{(HN(CH2)3O(CH2)2O(CH2)2 O(CH2)3NH)}☆

Abstract Reaction of N 3 P 3 Cl 6 with diethylene glycol bis-(3-aminopropyl)-ether (coded as 3O2O2O3) using a tolueneNa 2 CO 3 interface process leads to the MEGA-SPIRO (3O2O2O3) species neat. This chemical, C 10 H 22 N 5 O 3 P 3 Cl 4 , M r =493.03, crystallizes in the orthorhombic system, Pca 2 1 , a =15.453(3), b =13.978(2), c =9.818(2) A, V =2121(2) A 3 , Z =4, D X =1.55(1), D m =1.55(3) Mg m −3 , λ(Mo K α)=0.70926 A, F (000)=1016, T =291 K, R =0.038 for 1491 unique observed reflections and 250 variable parameters. The structure exhibits a spatial arrangement N 3 P 3 Cl 4 with HN(CH 2 ) 3 O(CH 2 ) 2 O(CH 2 ) 3 NH as a 16-membered loop on one phosphorus atom of the N 3 P 3 ring.

Crystal and molecular structure of the first dibino non-geminal macrocyclic dicyclophosphazene, & {;N3P3Cl4[HN(CH2)3O(CH2)2O(CH2)3NH]&};2

Abstract Reaction of N 3 P 3 Cl 6 with the 4,7-dioxadecane-1,10-diamine (coded as 3O2O3) using an Et 2 O/Na 2 CO 3 water interface process leads to the DIBINO non-geminal 30-membered macrocyclic dicyclophosphazene &{;N 3 P 3 Cl 4 [HN(CH 2 ) 3 O(CH 2 ) 2 O(CH 2 ) 3 NH]&}; 2 . This 30-crown-ether-like architecture crystallizes in the triclinic system, P 1 , a =9.019(6), b =9.224(5), c =11.542(8) A, α=94.87(4), β=95.97(4), γ=99.68(3)°, V =936(1) A 3 , D x =1.599 Mg m −3 , R =0.049 for 2862 unique reflections and 199 variable parameters. The structure exhibits a spatial arrangement of two N 3 P 3 Cl 4 with two [HN(CH 2 ) 3 O(CH 2 ) 3 O(CH 2 ) 3 NH] as bridges on different P atoms of N 3 P 3 rings. Moreover, the two N 3 P 3 rings are trans to the average plane of the 30-membered macrocycle (“chair” conformation).

Molecular orbitals and photoelectron spectra of some titanium(IV) organometallic compounds

Abstract The photoelectron spectra of some titanium(IV) organometallic compounds are reported, and the data and the bonding in the compounds are discussed with the aid of extended CNDO/2 calculations.

Crystal and molecular structure of the spiransa and dispiransa cyclophosphazenic derivatives from spermidine and spermine, N3P3Cl3[HN(CH2)3N(CH2)4NH] and N3P3Cl2[HN(CH2)3N(CH2)4N(CH2)3NH]☆

Abstract Reaction of N 3 P 3 Cl 6 with spermidine and spermine in protic solvents such as CHCl 3 proceeds cleanly to yield the SPIRANSA, N 3 P 3 Cl 3 [HN(CH 2 ) 3 N(CH 2 ) 4 NH], and the DISPIRANSA, N 3 P 3 Cl 2 [HN(CH 2 ) 3 N(CH 2 ) 4 N(CH 2 ) 3 NH], derivatives, respectively. These two chemicals crystallize in orthorhombic systems. SPIRANSA: Pbcn, a = 20.206(3), b = 18.107(3), c = 9.944(2)A, V = 3638 A 3 , Z = 8, D X = 1.56(1) Mg m −3 , R = 0.067 for 2880 unique reflections and 226 variable parameters. DISPIRANSA: Pmn 2 1 , a = 13.653(6), b = 8.467(5), c = 7.297(2)A, V = 843.5 A 3 , Z = 2, D X = 1.73(1) Mg m −3 , R = 0.045 for 736 unique reflections and 117 variable parameters. These two structures exhibit spermidino and spermino ligands grafted on the N 3 P 3 ring in a merged bicyclic SPIRANSA (i.e. a fusion of one SPIRO loop and of an ANSA arch) and a merged tricyclic DISPIRANSA (i.e. a fusion of two SPIRO loops and of an ANSA arch) configurations, respectively.