Marek M. Kubicki

Reactivity of CuI and CuBr toward Et2S: a reinvestigation on the self-assembly of luminescent copper(I) coordination polymers.

CuI reacts with SEt(2) in hexane to afford the known strongly luminescent 1D coordination polymer [(Et(2)S)(3){Cu(4)(mu(3)-I)(4)}](n) (1). Its X-ray structure has been redetermined at 115, 235, and 275 K in order to address the behavior of the cluster-centered emission and is built upon Cu(4)(mu(3)-I)(4) cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging SEt(2) ligands. However, we could not reproduce the preparation of a coordination polymer with composition [(Et(2)S)(3){Cu(4)(mu(3)-Br)(4)}](n) as reported in Inorg. Chem. 1975, 14, 1667. In contrast, the autoassembly reaction of SEt(2) with CuBr results in the formation of a novel 1D coordination polymer of composition [(Cu(3)Br(3))(SEt(2))(3)](n) (2). The crystal structure of 2 has been solved at 115, 173, 195, and 235 K. The framework of the luminescent compound 2 consists of a corrugated array with alternating Cu(mu(2)-Br)(2)Cu rhomboids, which are connected through two bridging SEt(2) ligands to a tetranuclear open-cubane Cu(4)Br(4) SBU, ligated on two external Cu atoms with one terminal SEt(2). The solid-state luminescence spectra of 1 and 2 exhibit intense halide-to-metal charge-transfer emissions centered at 565 and 550 nm, respectively, at 298 K. A correlation was also noted between the change in the full width at half-maximum of the emission band between 298 and 77 K and the relative flexibility of the bridging ligand. The emission properties of these materials are also rationalized by means of density functional theory (DFT) and time-dependent DFT calculations performed on 1.

A strategic approach to the synthesis of functionalized spirooxindole pyrrolidine derivatives: in vitro antibacterial, antifungal, antimalarial and antitubercular studies

A series of spiro[pyrrolidin-2,3′-oxindoles] has been synthesized by exo-selective 1,3-dipolar cycloaddition reaction of a stabilized azomethine ylide, generated in situ by thermal [1,5]-prototropy, across various (E)-3-arylidene-1-phenyl-pyrrolidine-2,5-diones. The stereochemistry of these N-heterocycles has been confirmed using an X-ray diffraction study. To rationalize the observed regio- and stereoselectivity, DFT calculations at the B3LYP/6-31G(d,p) level were employed. It was found that this reaction preferentially affords the kinetic product. The compounds have been screened for their in vitro antibacterial, antifungal, antimalarial and antitubercular activities. Several compounds exhibited good activities comparable to those of established standard drugs.

Synthesis, Structure of Nitrogen-Containing Phosphinogold(I) Ferrocenes. In vitro Activity against Bladder and Colon Carcinoma Cell Lines.

The gold salt [(tht)AuCl] was reacted with [1-N,N-dimethylaminométhyl-2-diphenylphosphino]ferrocene (1) forming the bimetallic derivative 4. The reaction of methyl iodide and tetramethylammonium bromide on the chloride 4 produced the ammonium salt 5 and the bromide 6 respectively. New aminophosphines 2 and 3, which represent two of the rare phosphorylated metallocenes containing P(III)-N bond have also been coordinated to gold(I) to form 7 and 8. The presence of the ethoxy group in 7 provides evidence for the lability of one nitrogen-phosphorus bond. The X-ray structure of compounds 4 and 7 have been established. Both crystallize in space group P21/c, monoclinic, with a = 11.095(2) Å, b = 12.030(3) Å, c = 17.763(4) Å, β= 94.02(2)∘, Z = 4 for 4 and a = 14.863(3) Å, b = 8.036(5)Å, c = 18.062(5)Å, β =101.64(1)°, Z = 4 for 7. 197Au Mössbauer data are in good agreement with those for other linear P-Au-Cl containing complexes. The compounds were evaluated for in vitro anti-tumour activity against two human tumours. Differential cytotoxicity was observed with activity comparable to cisplatin, with the exception of one compound which was significantly more cytotoxic.

Application de la RMN du 95Mo a l'etude d'organo-complexes carbonyles du molybdene

Abstract Molybdenum-95 NMR spectra of a variety of cyclopentadienylmolybdenum(II) carbonyl species are reported. Shielding of the 95 Mo nucleus increases in the sequences (i) (η 5 -C 5 H 5 )Mo(CO) ~ (η 5 -C 5 H 5 )Mo(CO) 2 5 -C 5 H 5 )Mo(CO) 3 , (ii) chelate 4-ring 5 -C 5 H 5 )(CO) 3 MoCl 5 -C 5 H 5 )(CO) 3 MoBr 5 -C 5 H 5 )(OC) 3 MoI. The results are discussed in terms of general applications of the technique to organomolybdenum chemistry.

Regio- and Stereoselective Synthesis of Spiropyrrolizidines and Piperazines through Azomethine Ylide Cycloaddition Reaction

A series of original spiropyrrolizidine derivatives has been prepared by a one-pot three-component [3 + 2] cycloaddition reaction of (E)-3-arylidene-1-phenyl-pyrrolidine-2,5-diones, l-proline, and the cyclic ketones 1H-indole-2,3-dione (isatin), indenoquinoxaline-11-one and acenaphthenequinone. We disclose an unprecedented isomerization of some spiroadducts leading to a new family of spirooxindolepyrrolizidines. Furthermore, these cycloadducts underwent retro-1,3-dipolar cycloaddition yielding unexpected regioisomers. Upon treatment of the dipolarophiles with in situ generated azomethine ylides from l-proline or acenaphthenequinone, formation of spiroadducts and unusual polycyclic fused piperazines through a stepwise [3 + 3] cycloaddition pathway is observed. The stereochemistry of these N-heterocycles has been confirmed by several X-ray diffraction studies. Some of these compounds exhibit extensive hydrogen bonding in the crystalline state. To enlighten the observed regio- and stereoselectivity of the [3 + 2] cycloaddition, calculations using the DFT approach at the B3LYP/6-31G(d,p) level were carried out. It was found that this reaction is under kinetic control.

New 1,1%- or 1,2- or 1,3-bis(diphenylphosphino)ferrocenes

The syntheses of ferrocenyl phosphines with bulky substituents are reported using the reaction between FeCl2 and the suitably substituted cyclopentadienyl salts, LiC5H3-1,3-(PPh2)2, LiC5H3-1-PPh2-3- t Bu, LiC5H2-1,2-(PPh2)2-4- t Bu. This strategy leads to bi-, tri- and tetraphosphines, which cannot be obtained by the other access paths used to prepare substituted ferrocenes. [C5H3-1,3(PPh2)2](C5H5)Fe, [C5H3-1-PPh2-3- t Bu]2Fe racemic and meso and [C5H2-1,2-(PPh2)2-4- t Bu](C5H5)Fe have been characterized by single-crystal X-ray diffraction studies.

Metalloligands containing samarium(III). Access to binuclear f-metal (samarium)-d-metal (rhodium) complexes

The synthesis of the new dimethylphosphinotetramethylcyclopentadiene HC5Me4PMe2 and of its potassium salt KC5Me4PMe2 are reported. Reactions of this potassium salt (as well as of the known LiC5H4PPh2 and KC5Me4PPh2) with [(COT)SMCl(THF)2]2 gave a series of metalloligands (COT)Sm(C5R4PR′2(THF)n (R = H or Me; R′ = Me or Ph; n = 0 or 2; COT = η8-cyclooctatetraenyl; THF = tetrahydrofuran). The X-ray crystal structure of (COT)Sm(C5H4PPh2(THF)2 is described. These metallophosphines reacted quantitatively with (C5H5)Rh(CO)2 to give phosphido-bridged bimetallic samarium(III)-rhodium(I) complexes (COT)Sm(μ-C5R4PR′2)Rh(C5H5)(CO) (R = H or Me; R′= Me or Ph). Crystal data: C33H38O2PSm, triclinic, P1 a = 8.606(2), b = 11.458(3), c = 14.632(2) A, α = 87.09(2), β = 86.93(2), γ = 87.18(2)°, V = 1437.3 A3, Z = 2, Dx = 1.497 g cm−3, m = 21.305 cm−1, λ (Mo-Kα) = 0.71073 A, R = 0.036.

Formation of an unprecedented (CuBr)5 cluster and a zeolite-type 2D-coordination polymer: a surprising halide effect

A unique pentanuclear cluster within a zeolite-type polymer ([Cu5(μ4-Br)(μ3-Br)2(μ2-Br)2](μ2-MeSPr)3)n (1; void space >81%) and a luminescent 1D ([Cu(μ3-I)]4(MeSPr)3)n polymer, 2, are formed when MeSPr reacts with CuBr and CuI.

Réactions d'insertion du cyanoacétylène et du dicyanoacétylène dans les deux liaisons métalhydrogène des dihydrures [(C5H5)2MH2] (M Mo ou W)

Abstract Only alkyne or alkene insertion reactions into one MH bond of [(C 5 H 5 ) 2 MH 2 ] (M  Mo or W) have been reported up to now. The insertion of alkynes with low steric hindrance, cyanoacetylene (HCCCN) and dicyanoacetylene (NCCCCN) into both MH of [(C 5 H 5 ) 2 MH 2 ] bonds are described in this paper. The first, as well as the second insertion of the same alkyne (either HCCCN or NCCCCN) is stereoselective. The (C 5 H 5 ) 2 M(H)AAH or (C 5 H 5 ) 2 M(AAH) 2 complexes are formed. In the case of mixed diinsertion complexes, ([(C 5 H 5 ) 2 M(σ-C 3 H 2 N)(σ-C 4 HN 2 )]) containing both cyanoacetylene and dicyanoacetylene, the geometry of the final products depends on the order of addition of the reactants. Thus, the insertion of (HCCCN) into [(C 5 H 5 ) 2 MH(σ- trans -C(CN)CHCN)] is stereoselective, while in the reaction of (NCCCCN) with [(C 5 H 5 ) 2 MH(σ-C(CN)CH 2 ] two stereoisomers [(C 5 H 5 ) 2 M(σ- trans - and - cis -C(CN)CHCN)(σ-C(CN)CH 2 )] are formed. Insertions of cyanoacetylene and dicyanoacetylene into a MH bond of (C 5 H 5 ) 2 M(H)AAH complexes (AA  HCCCF 3 , CH 3 O 2 CCCCO 2 CH 3 , NCCHCHCN, CH 3 O 2 CCHCHCO 2 CH 3 ) are also reported. The stereochemistry of the various complexes is proposed on the basis of 1 H and 13 C NMR spectra, and the mechanisms of the various insertion reactions are discussed.

FERROCENIC POLYPHOSPHINES AND POLYTHIOETHERS : SYNTHESIS, REACTIVITY AND STRUCTURE

Abstract The new ferrocenic polyphosphines [C 5 Me 3 -1,2-(PPh 2 ) 2 ](C 5 H 5 )Fe 2 , [C 5 Me 3 -1,2-(PPh 2 ) 2 ] 2 Fe 3 , [C 5 Me 3 -1,2-(PPh 2 ) 2 ][C 5 Me 4 (PPh 2 )]Fe 4 and polythioethers [C 5 Me 3 -1,2-(SCH 2 CH 2 CH 3 )2] 2 Fe 6 and [C 5 Me 3 -1,2-(SCH 2 CH 2 CH 3 ) 2 ](C 5 H 5 )Fe 7 have been prepared. The X-ray crystal structures of 3 and 6 have been determined. Some aspects of the reactivity of compounds 2 , 3 and 4 are reported (P(III)→P(V) transformation, chelating properties) as well as the X-ray structure of [C 5 Me 3 -1,2-(PPh 2 ) 2 W(CO) 4 ](C 5 H 5 )Fe 15 .