Metallacyclic complexes of iridium

Bezman, Susan A.; Bird, Peter H.; Fraser, Alan R.; Osborn, John A.

doi:10.1021/ic50214a035

Cited by 30 publications

(14 citation statements)

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“…All dimensions within the dibutphos ligand are normal, and they and other dimensions in the cation correspond well with those in related complexes (17,27,28). The geometry of the norbornadiene ligand is unexceptional (29)(30)(31)(32)(33)(34)(35)(36)(37)(38)(39)(40)(41)(42)(43)(44). Weighted leastsquares planes and selected torsion angles have been deposited as Tables SVI and S V I I .~…”

Section: Resultssupporting

confidence: 60%

Chiral phosphine ligands in asymmetric synthesis. IV. Hydrosilation of ketones, and the structure of (bicyclo[2.2.1]hepta-2,5-diene)[N,N-dimethyl-1(R)-(o-(bis(tert-butyl)phosphino)phenyl)ethylamine]rhodium(I) perchlorate

McKay¹,

Payne²

1986

Can. J. Chem.

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. Can. J. Chem. 64, 1930Chem. 64, (1986. The crystal structure and absolute configuration of (bicyclo[2.2.1]hepta-2,5-diene)[N,N-dimethyl-1(R)-(o-(bis(tertbutyl)phosphino)phenyl)ethylamine]rhodium(I) perchlorate, [Rh(R-dibutphos)(C7H8)]C104, have been determined from threedimensional X-ray data collected by counter methods. The complex crystallizes in the orthorh~~mbic space group P212121 with four formula units in a cell of dimensions a = 15.773(3), b = 18.660(4), and c = 8.990(3) A. Full-matrix least-squares techniques on F, using 2257 reflections with F > 1.5u(F), were used to refine the structure to a final agreement factor of R1 = 0.042. The cation displays a small tetrahedral distortion from :quare planar geometry (if the diene is viewed as a bidentate ligand) with Rh-P and Rh-N distances of 2.398(2) and 2.212(6) A, respectively. The absolute configuration of the aminophosphine ligand was determined to be R by the Bijvoet method. The six-membered chelate ring adopts a 6 twist-boat conformation with the methyl substituent of the chiral C atom axially disposed. Rh complexes of the aminophosphine ligand were shown to catalyze the homogeneous hydrosilation of prochiral ketones, but failed to produce an optical bias in any of systems investigated. (3) A. On a rCsolu la structure par la mCthode des moindres carr6s (matrice entibre sur F) et on l'a affinCe jusqu'a une valeur de R, = 0.042 en se basant sur 2257 rkflexions avec F > 1,5u(F). Le cation existe dans un forme tCtraCdrique 16gbrement dCformCe de la gComCtrie plan carrC (si l'on consjdkre le dikne comme un ligand bidentate) et les distances Rh-P et Rh-N sont respectivement Cgales a 2,398(2) et 2,212(6) A. Utilisant la mCthode de Bijvoet, on a determink que la configuration absolue du ligand aminophosphie est R. Le chClate a six chainons adopte une conformation 6 bateau deform6 dans lequel le substituant mCthyle de I'atome de carbone chiral est disposC dans la position axiale. On a dCmontrC que les complexes de Rh avec I'aminophosphine catalysent I'hydrosilation homogbne des cttones prochirales; toutefois, dans les systbmes CtudiCs, il n'y a pas de formation prCfCrentielle de l'un des isomkres optiques.[Traduit par la revue]

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Section: Resultssupporting

confidence: 60%

Chiral phosphine ligands in asymmetric synthesis. IV. Hydrosilation of ketones, and the structure of (bicyclo[2.2.1]hepta-2,5-diene)[N,N-dimethyl-1(R)-(o-(bis(tert-butyl)phosphino)phenyl)ethylamine]rhodium(I) perchlorate

McKay¹,

Payne²

1986

Can. J. Chem.

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“…Transition-metal-catalysed cyclo-oligomerizations of alkenes are known to proceed via metallacyclic intermediates and in some cases such complexes have been isolated (Stockis & Hoffmann, 1980). By subsequent thermolysis or substitution reactions of these species catalytic cycles have been simulated (Doyle, McMeeking & Binger, 1976;Binger & Doyle, 1978;Bezman, Bird, Frazer & Osborn, 1980). Oxidative couplings of alkenes with low-valent transition-metal complexes normally give fivemembered metallacycles.…”

mentioning

confidence: 99%

“…Oxidative couplings of alkenes with low-valent transition-metal complexes normally give fivemembered metallacycles. Only for rhodium(I) and iridium(I) complexes (Cetinkaya, Binger & Krfiger, 1982;Bezman et al, 1980) has the isolation of sevenand eight-membered metallacycloalkanes been achieved. Unfortunately the use of rhodium(I) and iridium(I) complexes as catalysts for the cyclo-* To whom correspondence should be addressed.…”

mentioning

confidence: 99%

“…While iridium(I) complexes show no activity at all (Bezman et al, 1980), rhodium(I) complexes only catalyse the oligomerization of 8,9,10-trinorbornadiene (Katz, Acton & Paul, 1969). In contrast, a number of activated alkenes are cyclo-oligomerized smoothly and selectively in the presence of palladium(0) complexes (Binger, Cetinkaya, Doyle, Germer & Schuchardt, 1979).…”

mentioning

confidence: 99%

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Structure of a nine-membered palladacycloalkane, bis[dimethyl(phenyl)phosphine]-3,3,6,6,9,9,13,13-octamethyl-anti,syn,anti,syn-11-palladapentacyclo[10.1.0.02,4.05,7.08,10]tridecane, C36H54P2Pd

Büch¹,

Krüger²

1984

Acta Crystallogr C

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Abstract. Mr=654.8, triclinic, P1, a= 11.236 (2), b= 11.774 (2), c= 14.682 (2) A,, ct= 74.01 (2), fl= 86.92 (2), 7= 75.59 (2) ° , V= 1808/~3, Z=2, D x = 1.203 Mg m -3, 2(Mo Kct) = 0.71069/k, fl = 0.611mm -1, F(000) = 692, T= 293 K. Final R = 0.031 for 6282 unique observed X-ray diffractometer data. The nine-membered metaUacycle contains a slightly distorted square-planar Pd atom coordinated by two phosphine ligands. The four cyclopropane rings impose steric rigidity on the ring, whose conformation resembles the all-cis boat conformation of 1,3,5,7-cyclononatetraene rather than the twisted-boat-chair and twisted-chair-boat forms calculated for cyclononane. There are no short intermolecular distances.

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“…This structure determination supplements the mechanistic details of a kinetic study concerning the oxidative addition of CH3I to [Ir(fldiketone)(cod)] complexes. Bond distances and angles can be compared with relevant data in facIr(CH3)3PMe2Ph)3 (Lundquist, Folting, Huffman & Caulton, 1988), a partly metallacyclic norbornadiene complex [Ir(C7Ha)3(acac)] (Bezman, Bird, Fraser & Osborn, 1980), a tetrafluorobenzobarrelene complex [Ir(I)2(TFB)(phen)]C104. (CH3)2CO (Oro, Carmona & Esteruelas, 1986) and [Ir3(H)(/z3-S)2(cod)3(PMe3)] (Bright, Jones, Koschmieder & Nunn, 1988 …”

Section: Mann 1968) and Anomalous-dispersion Corrections From Internmentioning

confidence: 99%

(η-1,5-Cyclooctadiene)iodomethyl(2,4-pentanedionato-O,O')iridium(III)

Basson¹,

Leipoldt²,

Purcell³

et al. 1989

Acta Crystallogr C

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Metallacyclic complexes of iridium

Cited by 30 publications

References 0 publications

Chiral phosphine ligands in asymmetric synthesis. IV. Hydrosilation of ketones, and the structure of (bicyclo[2.2.1]hepta-2,5-diene)[N,N-dimethyl-1(R)-(o-(bis(tert-butyl)phosphino)phenyl)ethylamine]rhodium(I) perchlorate

Chiral phosphine ligands in asymmetric synthesis. IV. Hydrosilation of ketones, and the structure of (bicyclo[2.2.1]hepta-2,5-diene)[N,N-dimethyl-1(R)-(o-(bis(tert-butyl)phosphino)phenyl)ethylamine]rhodium(I) perchlorate

Structure of a nine-membered palladacycloalkane, bis[dimethyl(phenyl)phosphine]-3,3,6,6,9,9,13,13-octamethyl-anti,syn,anti,syn-11-palladapentacyclo[10.1.0.02,4.05,7.08,10]tridecane, C36H54P2Pd

(η-1,5-Cyclooctadiene)iodomethyl(2,4-pentanedionato-O,O')iridium(III)

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