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Journal of Organometallic Chemistry

journal homepage: www.elsevier .com/locate/ jorganchem

Volume 695, Issues 12-13, 1 June 2010

Contents

COMMUNICATION

Mitsushiro Nomura, Hiroki Oguro,Kazuaki Maeshima, Suguru Iida,Satoshi Horikoshi, Toru Sugiyama,Akira Sugimori, Masatsugu Kajitani

J. Organomet. Chem. 695 (2010) 1613

Aromatic [CpCo(S2C2(R)(H))] complexes(R ¼ Me and Ph) reacted with 2,20-diben-zothiazolyl disulfide (R’SSR’ (R0 ¼ 2-ben-zothiazolyl)) as a sulfur-centered radicalsource to form some radical substitution

Elsevier B.V.doi:10.1016/S0022-328X(10)00272-X

products by 2-benzothiazolylthiyl radical(R0S�). The R0S� radical was substituted onthe dithiolene ring or on the Me group(S-substituted products). An N-substitutedproduct was also formed by a nitrogen-centered radical that is a resonant speciesof the 2-benzothiazolylthiyl radical. Con-ventional heating, photochemical andmicrowave-enhanced reactions were per-formed.

REGULAR PAPERS

Laurent Plasseraud, Danielle Ballivet-Tkatchenko, Hélène Cattey,Stéphane Chambrey, Rosane Ligabue,Philippe Richard, Rudolph Willem,Monique Biesemans


The synthesis of the decakis(di-n-butyltin(IV)) oxocluster, (R2SnO)6[(R2SnOR0)2

(CO3)]2 (R ¼ C4H9, R0 ¼ CH3), as well as itsreactivity toward organic carbonates andits formation mechanism from R2SnOunder supercritical CO2 conditions areexplored and supported by IR, NMR (solu-tion and solid-state), and X-ray investiga-tions.

Akella Sivaramakrishna, Banothile C.E. Makhubela, John R. Moss, GregoryS. Smith


Large 19- and 21-membered plati-nacycloalkane compounds were synthe-sized through the ring closing metathesisreaction of bis(1-alkenyl)platinum(II) coml-pexes using Grubbs’ catalysts. Reactivitystudies of the title compounds with

elemental sulfur, carbon monoxide andmethyl iodide were also investigated.

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Contentsiv

Mohammed H. Alamiry, Conor Long,Padraig P. Fidgeon, Mary T. Pryce


The structure of (h-Aniline)Cr(CO)3 ischanged by annealing the crystallinematrix in low temperature matrix isolationexperiments. The reduced hapticity species

produced in this process undergoescomplete decarbonylation following low-energy irradiation. DFT calculationssuggest that the singletetriplet energy gapis smaller for the reduced hapticity speciescompared to (h6-Aniline)Cr(CO)3.

Astrid Malassa, Christine Agthe,Helmar Görls, Manfred Friedrich,Matthias Westerhausen


The di(2-pyridylmethyl)amides showa rather unique redox chemistry in thevicinity of late transition metals. Theseligands can be deprotonated at the

methylene fragments, initiating theformation of 1,3-di(2-pyridyl)-2-azaallylanions.

Eliano Diana, Edoardo Marchese


Vibrational analysis fromDFTcalculation ofC6F4Hg2 fragment: a “fingerprint” patternfor perfluorinated aromatic organomercu-rial.

Patrick Bippus, Anja Molter,David Müller, Fabian Mohr


The reaction of hydrazine hydrate withKSeCN and cyclohexanone in acidicaqueous ethanol gives cyclohexanoneselenosemicarbazone. This was converted

into various functionalised selenosemi-carbazones by treatment with aldehydes.Salicylaldehyde selenosemicarbazone andits 1,2-naphthyl-derivative were preparedand reacted with some Pd(II) and Pt(II)phosphine complexes. In these complexesthe ligands act as tridentate, dianionic[SeeNeO]2� ligands.

Contents v

Me3Si OSiMe3
Akinobu Naka, Shinsuke Ueda,Hiroki Fujimoto, Toshiko Miura,Hisayoshi Kobayashi, Mitsuo Ishikawa

The cothermolysis of pivaloyl- and ada-mantoyltris(trimethylsilyl)germane (1 and

2) with methyl vinyl ketone and acroleinat 120 �C gave the respective sixememberedering compounds. At 140 �C,the same reactions afforded acylbis(trime-thylsilyl)germanes arising from ringeopening of the sixememberederingcompounds as the main products.

CH

C

O

R2H2C

1. R1 = t-Bu2. R1 = Ad

Me3Si

Me3Si

Me3Si

O

R1 +

Ge

H2CGe C

C C

O

CMe3Si R1

H R2R2 = Me, H

3. R1 = t-Bu, R2 = Me 4. R1 = Ad, R2 = Me5. R1 = t-Bu, R2 = H

6. R1 = Ad, R2 = H

120°C

3 - 6

7 - 10

Ge

H2C O

C

Me3Si

Me3Si R1

H R2

O SiMe3

Ge

H2C

C C C C

O

C

Me3Si

Me3Si R1

H R2

O

SiMe3

140°C

2+
Kenichi Ogata, Toshinori Nagaya, Shin-ichi Fukuzawa

An binuclear iridium(III) and rhodium (III)complex bearing a methylnaphthalene-linked N-heterocyclic carbene wasprepared by the reaction of [Cp*MCl2]2 (M

¼ Ir, Rh) with silver NHC complex. Ontreatment of the binuclear neutralcomplexes with AgPF6, the Cl-bridgedcationic iridium and rhodium complexeswere formed. The cationic iridium complexcould be applied to the intramolecularhydroamination of 2-ethynylaniline to givethe corresponding indole compound.

NNR

NN

RM M

Cl

Cl

2PF6-

2eq. AgPF6R

N N

MCl

ClR

NN

MCl

Cl

CH2Cl2/acetone r.t.

10 eq Et SnH 10 eq Et SnH
Xiangai Yuan, Siwei Bi, Lingjun Liu,Min Sun, Jiayong Wang

A computational study with Becke3LYP ofDFT was carried out to investigate theligand exchange reaction mechanismsof Cp(CO)FeH(EEt3)(E0Et3) with (HEEt3)(E, E0 ¼ Si, Ge, Sn).

FeEt3SnH

GeEt3CO

FeEt3SnH

SnEt3CO

FeEt3SiH

GeEt3CO

3

603

60

Sergey V. Timofeev, Elena A. Prikaznova,Zoya A. Starikova, Ivan A. Godovikov,Vladimir I. Bregadze


Halogenation of charge-compensated nido-carborane [9-Me3N-7,8-C2B9H11] (1) withelemental halogens X2 (X ¼ Cl, Br, I) wasinvestigated. Structures of [11-I-9-Me3N-7,8-C2B9H10], [6,11-Br2-9-Me3N-7,8-C2B9H9]

and [1,6,11-Br3-9-Me3N-7,8-C2B9H8] wereestablished using single crystal X-raydiffraction.

Contentsvi

Takeshi Ishihara, Hoang The Ban,Hideaki Hagihara, Takeshi Shiono


0
Dennis Troegel, W. Peter Lippert,Frank Möller, Christian Burschka,Reinhold Tacke

A series of novel bifunctional silacyclobu-tanes and silacyclopentanes of the formulatypes (CH2)nSi(CH2X)2 (e.g. I) and (CH2)nSi(CH2X)CH2X0 (e.g. II∙HCl) (n ¼ 3, 4; X,

X ¼ functional groups) was synthesized,starting from (CH2)3Si(CH2Cl)2 and(CH2)4Si(CH2Cl)2, respectively. Thedifferent reactivity profiles of the analo-gous silacyclobutanes and silacyclo-pentanes were compared.

CH3
André L. Bogado, Marília I.F. Barbosa,Gezimar D. de Souza, Marília A. Trappi,Edson R. Filho, Leonardo T. Ueno,Antonio E.H. Machado, Alzir A. Batista

During the reaction between [{RuCl(dppb)}2-(m-Cl)2] and ethyldiazoacetate

(EDA) an in situ neutral carbene complexwas observed in a methylene chloridesolution with vigorous N2 evolution. Thisreaction was investigated by ESI-MS anal-ysis, NMR and DFT-calculation whichsuggests the formation of a mononuclearcarbene containing ruthenium as product,[RuCl2(dppb)(]CHC(O)OCH2CH3].

RuCl

RuCl

Cl

PP

Cl

PP

C

RuCl P

PCl

HCO O

CH2

EDA / CH2Cl2

- N2

EDA = ethyldiazoacethate

Abdeladim Guermoune,Driss Cherqaoui, Abdellah Jarid,Joel F. Liebman


[HFe(CO)4(B2H5)] complex exhibits anunusual borane coordination. This coordi-nation mode is reproduced in Ru and Oscongeners. The decomposition to Fe(CO)5and B2H6 involves a three-centres-bridged-hydrogen structure. The spin multiplicity

of Fe(CO)4 seems to take part of thisdecomposition. A clear structural study isproposed.

Contents vii

Manoj Trivedi, R. Nagarajan,Abhinav Kumar, Nigam P. Rath


Reactions of vanadium(IV) complexes with2,6-dicarboxamido-2-pyridylpyridineligand results in the formation of oxido-bridged dinuclear vanadium complex[apyH]2[{VOL}2(m-O)2].2H2O [1]. Molecular

structure of 1 has been determined bysingle-crystal X-ray analysis and exhibitedefficient catalytic activity toward epoxida-tion of cis-cyclooctene with tert-buthylhy-droperoxide (TBHP) selectively.

Zekeriya Bıyıklıo�glu, Salih Zeki Yıldız,Halit Kantekin


The metal-free phthalocyanine 2 wassynthesized from the 4,5-bis(1,4,7,10-tet-raoxacyclododecan-2-ylmethoxy)phthalo-nitrile 1 in the presence of a strong basein n-pentanol. The synthesis of metalloderivatives [Ni(II), Co(II), Cu(II)] of phtha-locyanines obtained from correspondingphthalonitrile derivative 1 and in the

presence of the anhydrous divalent metalsalts (NiCl2, CoCl2 and CuCl2) weredescribed. The thermal stabilities of themetal-free and metallophthalocyanineswere determined by thermogravimetricanalysis. These phthalocyanines were goodsoluble in organic solvents such as chlo-roform, dichloromethane, tetrahydrofuranand DMF. The products were characterizedby elemental analysis, IR, 1H NMR, UVevisand MS spectral data.

Magdalena Zyder, Teresa Szyma�nska-Buzar


Photochemically activated [Mo(CO)6]and [Mo(CO)4(h4-nbd)] are demonstratedto be good catalysts for the hydro-stannation of norbornadiene by stannylhydrides (nBu3SnH and Ph3SnH) to give

stannylnorbornene in ca. 100 % yield.The reaction was carried out at roomtemperature in n-heptane (20 cm3) withcontinued photolysis (2h) at Mo(CO)6:R3SnH:nbd ¼ 1:50:50.

Mo(CO)6, h

n-heptane, 2h, r.t.+ R3SnH

SnR3

SnR3+

R = nBu, Ph

NOTES

Neli Mintcheva, Makoto Tanabe,Kohtaro Osakada, Ivelina Georgieva,Tzvetan Mihailov, Natasha Trendafilova


The first dinuclear platinum complex con-taining a (m-O,O)-bridging silsesquioxanateligand was synthesized. The molecularstructure was proposed by DFT calculationsand NMR study.

R=c-C5H9

OSi

O

Si O Si

O

SiSi

O

Si OSi

O

O O

R

R

RR

R

RR

OPt

Ph

PEt3

Et3P

OH

OPt

Ph

PEt3

Et3P

Contentsviii

R R CHO R
Chan Sik Cho, Hyo Bo Kim,Sang Yeon Lee

2-Bromocyclohex-1-enecarbaldehydes arecarbonylatively cyclized with anilines

under CO in the presence of a palladiumcatalyst to furnish hydroisoindol-1-ones.

A : PBr3, DMF, CHCl3B : PdCl2(PhCN)2, ArNH2, CO, DMF

O BrN

O

ArA B

Tomoyuki Mochida, Kenji Yoza


The first-order phase transition at 257 K indecamethylferroceneeacenaphthenequin-one is associated with ordering of thedisordered pentamethylcyclopentadienylrings in decamethylferrocene.

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