Regio- and Stereoselective Insertion Reactions of Thiiranes into Pt−Mn (or Re) Bond in Organoplatinum−Manganese or −Rhenium Heterodinuclear Complexes as Intermediates toward Desulfurization Reaction

Komiya, Sanshiro; Muroi, Shin-ya; Furuya, Masaki; Hirano, Masafumi

doi:10.1021/ja993185m

Cited by 28 publications

(19 citation statements)

References 16 publications

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“…for C 30 H 32 F 3 NO 3 P 2 PdS: C,50.61;H,4.53;N,1.97. Found: C,50.45;H,4.70 H NMR spectra for the reaction mixture of (dppe)MePd-Co(CO) 4 (1) with aziridine in THF-d 8 . Table 6 Thermodynamic parameters for the equilibrium of aziridine coordination to 1…”

Section: Synthesis Of [Pdme(aziridine)(dppe)] + [So 3 Cf 3 ] à (13)mentioning

confidence: 97%

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Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide

Tanaka

Hoh

Akahane

et al. 2007

Journal of Organometallic Chemistry

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Section: Synthesis Of [Pdme(aziridine)(dppe)] + [So 3 Cf 3 ] à (13)mentioning

confidence: 97%

“…for C 25 H 21 CoN 2 O 6 Pd: C,49.16;H,3.47;N,4.59. Found: C,49.42;H,3.64;N,4.17%. Molar electric conductivity K (THF, r.t.): 0.0199 S cm 2 mol À1 .…”

Section: Synthesis Of Heterodinuclear Organopalladium Complexes Havinmentioning

confidence: 98%

Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide

Tanaka

Hoh

Akahane

et al. 2007

Journal of Organometallic Chemistry

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“…The Mo moiety possesses a pseudosquare-pyramidal structure, which is similar to that of the known Mn(-I) anionic complex [Ph 4 P][Mn(CO) 5 ]. 10 The Pt-Mn bond distance (3.0337(8) Å ) in 1a is significantly longer than those observed in other heterodi-or heterotrinuclear complexes containing platinum and manganese, 11,12 suggesting effective steric repulsion between the Pt and Mn moieties. In fact, four ligands at Pt and the carbonyl ligands cis to Pt in Mn are placed in a staggered conformation in order to minimize their steric congestion.…”

mentioning

confidence: 91%

Visible Light Enhanced Selective Reductive Elimination of a Methylmanganese Complex from a Heterodinuclear Dimethylphenyl(4,4′-di-tert-butyl-2,2′-bipyridine)platinum−Pentacarbonylmanganese Complex

et al. 2009

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Novel visible light induced reductive elimination of a heterodinuclear triorganoplatinum-manganese complex, ( t Bu 2 bpy)Me 2 PhPt-Mn(CO) 5 , gives a methylmanganese complex, MnMe(CO) 5 , and a methylphenylplatinum complex, PtMePh( t Bu 2 bpy).Use of light energy in controlling the selectivity and activity of chemical reactions is a highly fascinating method, but it is in generally very difficult, since irradiation frequently causes homolytic bond cleavage, dissociation of ligands, etc. or sometimes even luminescence. 1,2 On the other hand, reductive elimination is one of the most important key steps in organotransition-metal chemistry in relation to transition-metalmediated organic reactions and catalyses. 3 Among them, C-C bond forming reductive elimination is the most well studied both experimentally 4 and theoretically. 5 Other reductive elimination processes involving hetero elements are also intrinsically of importance in various catalyses promoted by transition-metal complexes. 6 We previously reported the reversible alkyl group transfer reaction of heterodinuclear organotransition-metal complexes, 7 which is regarded as reductive elimination of an organotransition-metal complex from the dinuclear complex. We wish to report here novel visible light enhanced reductive elimination of a methylmanganese complex under ambient conditions from heterodinuclear triorganoplatinum-manganese complexes.A series of (2,2 0 -bipyridine)-or (4,4 0 -di-tert-butyl-2,2 0 -bipyridine)triorganoplatinum-manganese pentacarbonyl complexes were prepared by the simple metathetical reactions of the corresponding triorgano(nitrato)platinum(IV) species with sodium pentacarbonylmanganate in THF (eq 1).In these heterodinuclear complexes, a large R 2 group is always placed trans to Mn, probably due to steric hindrance between the square-planar Pt coordination plane and the four equatorial carbonyl ligands at Mn. 1a in THF shows two absorption bands at 533 (ε = 2900 M -1 cm -1 ) and 325 nm (ε = 15 000 M -1 cm -1 ), which are ascribed to MLCT bands from the HOMO orbital based on the Pt-Mn bond to the LUMO assignable to two empty π* orbitals of the bpy ligand. 8 Nakagawa, H.; Akita, M.; Inoue, K.; Sakai, M.; Fujii, M. Dalton Trans. 2008, 6709-6723 and references therein. (3) (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Laio, A.; Mohamed, F.; Krack, M.; Parrinello, M.; Milet, A. Organometallics 2007, 26, 1241-1249. (h) P erez-Rodrı´guez, M.; Braga, A. A. C.; Garcia-Melchor, M.; P erez-Temprano, M. H.; Casares, J. A.; Ujaque, G.; de Lera, A. R.; Alvarez, R.; Maseras, F.; Espinet, P. DFT calculations of 1a and 1c and their corresponding products,which were performed by using Spartan 06 Windows from Wavefunction, Inc. at the B3LYP/LACVP/6-31G* level of theory, reveal that reductive elimination of the former is endothermic but that of the latter is exothermic. The calculated wavelengths of two MLCT bands of 1a were 554 and 400 nm. See the Supporting Information.

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“…The Pt geometry is regarded as a square-planar by the bridging hydride and carbonyl carbon, and two phosphorus atoms of dppe, whereas the Mn has a near-perfect octahedral geometry generated from the m-H and the five CO's ligands. The PteMn distance for 3c is 2.686(2) Å, which is shorter than those for (Et 3 P) 2 Pt(m-H)(m-CO)Mn(CO) 4 (2.730(2) Å) [11] and (dppe)MePteMn(CO) 5 (2.795(2) Å) [20]. The PteP1 and PteP2 distances are 2.292(1) and 2.230(2) Å, respectively.…”

Section: Introductionmentioning

confidence: 98%

Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes

Komine

Kuramoto

Yasuda

et al. 2015

Journal of Organometallic Chemistry

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Regio- and Stereoselective Insertion Reactions of Thiiranes into Pt−Mn (or Re) Bond in Organoplatinum−Manganese or −Rhenium Heterodinuclear Complexes as Intermediates toward Desulfurization Reaction

Cited by 28 publications

References 16 publications

Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide

Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide

Visible Light Enhanced Selective Reductive Elimination of a Methylmanganese Complex from a Heterodinuclear Dimethylphenyl(4,4′-di-tert-butyl-2,2′-bipyridine)platinum−Pentacarbonylmanganese Complex

Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes

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