Dichloro and alkylchloro gallium derivatives of dichalcogenoimidodiphosphinate ligands: isolation of a spirogallium cation

Dichloro and chloromethyl Ga(III) complexes of general formulae [XClGa-eta2-{R2P(E)NP(E'R'2-E,E'}](X = Cl, R, R'= Ph, E, E'= O (1), S (2), Se (3); R = Ph, R'= OEt, E = O, E'= S (4); R = Me, R'= Ph, E, E'= S (5) and X = Me, E, E'= O (6), S (7), Se (8)) were synthesised by either metathesis reactions between GaCl3 and the potassium salt of the ligand (X = Cl) or by methane eliminations from in situ prepared GaMe2Cl and the protonated ligands LH (X = Me). Redistribution reaction of (3) in either CDCl3 or THF afforded the solvent-free tetracoordinate gallium spirocycle cation [Ga-{eta2-{Ph2P(Se)NP(Se)Ph2-Se,Se'})2]+ (9+). The molecular structures of complexes 2, 4, 5, 7 and 9(+) show non-planar gallacycle rings.     

Two types of intramolecular addition of an Al-N multiple-bonded monomer LAlNAr' arising from the reaction of LAl with N3Ar' (L = HC[(CMe)(NAr)]2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3)

The reaction of beta-diketiminated aluminum(I) monomer LAl with a large bulky azide N3Ar' (L = HC(CMeNAr)2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3) in the temperature range from -78 degrees C to room temperature affords two different isomers 2 and 3, which have been characterized by spectroscopic and X-ray structural analyses, as well as elemental analysis. The variable-temperature 1H NMR kinetic studies of this reaction indicate the existence of the monomer LAlNAr' (1) at low temperature and the thermal stability of the compounds increases in the order of 1 < 2 < 3.     

Terphenyl substituted derivatives of manganese(II): distorted geometries and resistance to elimination

Reaction of {Li(THF)Ar'MnI(2)}(2) (Ar' = C(6)H(3)-2,6-(C(6)H(2)-2,6-(i)Pr(3))(2)) with LiAr', LiC≡CR (R = (t)Bu or Ph), or (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) afforded the diaryl MnAr'(2) (1), the alkynyl salts Ar'Mn(C≡C(t)Bu)(4){Li(THF)}(3) (2) and Ar'Mn(C≡CPh)(3)Li(3)(THF)(Et(2)O)(2)(μ(3)-I) (3), and the manganate salt {Li(THF)}Ar'Mn(μ-I)(C(6)H(2)-2,4,6-(i)Pr(3)) (4), respectively. Complex 4 reacted with one equivalent of (C(6)H(2)-2,4,6-(i)Pr(3))MgBr(THF)(2) to afford the homoleptic dimer {Mn(C(6)H(2)-2,4,6-(i)Pr(3))(μ-C(6)H(2)-2,4,6-(i)Pr(3))}(2) (5), which resulted from the displacement of the bulkier Ar' ligand in preference to the halogen. The reaction of the more crowded {Li(THF)Ar*MnI(2)}(2) (Ar* = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2)) with Li(t)Bu gave complex Ar*Mn(t)Bu (6). Complex 1 is a rare monomeric homoleptic two-coordinate diaryl Mn(II) complex; while 6 displays no tendency to eliminate β-hydrogens from the (t)Bu group because of the stabilization supplied by Ar*. Compounds 2 and 3 have cubane frameworks, which are constructed from a manganese, three carbons from three acetylide ligands, three lithiums, each coordinated by a donor, plus either a carbon from a further acetylide ligand (2) or an iodide (3). The Mn(II) atom in 4 has an unusual distorted T-shaped geometry while the dimeric 5 features trigonal planar manganese coordination. The chloride substituted complex Li(2)(THF)(3){Ar'MnCl(2)}(2) (7), which has a structure very similar to that of {Li(THF)Ar'MnI(2)}(2), was also prepared for use as a possible starting material. However, its generally lower solubility rendered it less useful than the iodo salt. Complexes 1-7 were characterized by X-ray crystallography and UV-vis spectroscopy. Magnetic studies of 2-4 and 6 showed that they have 3d(5) high-spin configurations.     

The role of group 14 element hydrides in the activation of C-h bonds in cyclic olefins

Formally, triple-bonded dimetallynes ArEEAr [E = Ge (1), Sn (2); Ar = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2)] have been previously shown to activate aliphatic, allylic C-H bonds in cyclic olefins, cyclopentadiene (CpH), cyclopentene (c-C(5)H(8)) and 1,4-cyclohexadiene, with intriguing selectivity. In the case of the five-membered carbocycles, cyclopentadienyl species ArECp [E = Ge (3), Sn (4)] are formed. In this study, we examine the mechanisms for activation of CpH and c-C(5)H(8) using experimental methods and describe a new product found from the reaction between 1 and c-C(5)H(8), an asymmetrically substituted digermene ArGe(H)Ge(c-C(5)H(9))Ar (5), crystallized in 46% yield. This compound contains a hydrogenated cyclopentyl moiety and is found to be produced in a 3:2 ratio with 3, explaining the fate of the liberated H atoms following triple C-H activation. We show that when these C-H activation reactions are carried out in the presence of tert-butyl ethylene (excess), compounds {ArE(CH(2)CH(2)tBu)}(2) [E = Ge(8), Sn(9)] are obtained in addition to ArECp; in the case of CpH, the neohexyl complexes replace the production of H(2) gas, and for c-C(5)H(8) they displace cyclopentyl product 5 and account for all the hydrogen removed in the dehydroaromatization reactions. To confirm the source of 8 and 9, it was demonstrated that these molecules are formed cleanly between the reaction of (ArEH)(2) [E = Ge(6), Sn(7)] and tert-butyl ethylene, new examples of noncatalyzed hydro-germylation and -stannylation. Therefore, the presence of transient hydrides of the type 6 and 7 can be surmised to be reactive intermediates in the production of 3 and 4, along with H(2), from 1 and 2 and CpH (respectively), or the formation of 3 and 5 from 1. The reaction of 6 or 7 with CpH gave 3 or 4, respectively, with concomitant H(2) evolution, demonstrating the basic nature of these low-valent group 14 element hydrides and their key role in the 'cascade' of C-H activation steps. Additionally, during the course of these studies a new polycyclic compound (ArGe)(2)(C(7)H(12)) (10) was obtained in 60% yield from the reaction of 1,6-heptadiene and 1 via double [2 + 2] cycloaddition and gives evidence for a nonradical mechanism for these types of reactions.     

Reduction of terphenyl Co(II) halide derivatives in the presence of arenes: insertion of Co(I) into a C-F bond

Reduction of [(3,5-(i)Pr(2)-Ar*)Co(μ-Cl)](2) (3,5-(i)Pr(2)-Ar* = -C(6)H-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2)-3,5-(i)Pr(2)) with KC(8) in the presence of various arene molecules resulted in the formation of a series of terphenyl stabilized Co(I) half-sandwich complexes (3,5-(i)Pr(2)-Ar*)Co(η(6)-arene) (arene = toluene (1), benzene (2), C(6)H(5)F (3)). X-ray crystallographic studies revealed that the three compounds adopt similar bonding schemes but that the fluorine-substituted derivative 3 shows the strongest cobalt-η(6)-arene interaction. In contrast, C-F bond cleavage occurred when the analogous reduction was conducted in the presence of C(6)F(6), affording the salt K[(3,5-(i)Pr(2)-Ar*)Co(F)(C(6)F(5))] (4), in which there is a three-coordinate cobalt complexed by a fluorine atom, a C(6)F(5) group, and the terphenyl ligand Ar*-3,5-(i)Pr(2). This salt resulted from the formal insertion of a putative 3,5-(i)Pr(2)-Ar*Co species as a neutral or anionic moiety into one of the C-F bonds of C(6)F(6). Reduction of [(3,5-(i)Pr(2)-Ar*)Co(μ-Cl)](2) in the presence of bulkier substituted benzene derivatives such as mesitylene, hexamethylbenzene, tert-butylbenzene, or 1,3,5-triisopropylbenzene did not afford characterizable products.     

Characterization of Ar'Sn(micro-Br)Sn(Ar')CH2C6H4-4-Pri (Ar' = C6H3-2,6-Dipp2; Dipp = C6H3-2,6-Pri2): a stable structural analogue for a heavier group 14 element monobridged alkene isomer HM(micro-H)MH2 (M = Sn or Pb)

The title compound is the first stable structural analogue for the monobridged isomer of a heavier group 14 alkene analogue.     

Linear Tikhonov regularization against an edge field: an improved reconstruction algorithm in photothermal depth profilometry

This work introduces the concept of edge-field regularization into photothermal inverse depth profilometry problems. An edge field allows prior information concerning the depth location of material interfaces in a sample to be introduced into a Tikhonov regularization problem by a simple binary encoding. The edge-field regularization allows Nth-order Tikhonov stabilization constraints to be applied independently to multiple zones or segments of a depth profile between defined interface positions. This allows the reconstruction of continuous depth-profile information within known layers, without the globally imposed smoothing and edge oscillations of the classical regularization methods. This method successfully reconstructs both the amplitude of the interface discontinuities and the photothermal depth-contrast variations within the bounding edges, to a resolution limited by the resolving kernel for the underlying Nth-order Tikhonov constraint. The edge-field regularization dramatically reduces the errors associated with profiling photothermal contrast in bounded zones that are depth-displaced in the sample. Received: 19 September 2002 / Published online: 5 May 2003 RID="*" ID="*"Corresponding author. Fax: +1-514/398-3797, E-mail: joan.power@mcgill.ca