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![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Peripheral Palladium(II) and Platinum(II) Complexes of Bis(dimethylamino)porphyrazine
Steven J. Lange1, Hanlin Nie, Charlotte L. Stern
1Departments of Chemistry, Northwestern University, Evanston, Illinois 60208, and Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, U.K.
Abstract:
The unsymmetrical porphyrazine (tetraazaporphyrin) bearing a single peripheral bis(dimethylamino) functionality, Mg[pz(NMe(2))(2)(Pr)(6)], was prepared by base-catalyzed cross condensation of dipropyl maleonitrile (in excess) with dimethylamino maleonitrile. The freebase (2H[pz(NMe(2))(2)(Pr)(6)]) and centrally metalated forms (M[pz(NMe(2))(2)(Pr)(6)]; M = Ni(II), Cu(II), Mn(III)) were prepared by treatment of Mg[pz(NMe(2))(2)(Pr)(6)] with trifluoroacetic acid and then the appropriate metal salt. PdCl(2) and PtCl(2) were coordinated to the peripheral bis(dimethylamino) chelates, yielding the bimetallic complexes, M[pz(NMe(2))(2)(Pr)(6)]M'Cl(2) (M = Ni, Cu; M' = Pd, Pt). The heteroleptic [N(2)-Pd-S(2)]-capped porphyrazines were prepared readily by substituting the chloride ions of M[pz(NMe(2))(2)(Pr)(6)]PdCl(2) with the dithiolene chelates, maleonitriledithiolate (mnt(2)(-)), benzenedithiolate (bdt(2)(-)), and 1,3-dithiole-2-one-4,5-dithiolate (dmid(2)(-)). The [N(2)-Pt-S(2)] complexes were prepared by reaction of M[pz(NMe(2))(2)(Pr)(6)]PtCl(2) with the dialkyltin-protected dithiolates dibutyltin(toluene-3,4-dithiolate) and dibutyltin(dmit). The peripheral heteroleptic [N(2)-M'-S(2)] core was found to be electroactive for electron-rich dithiolene ligands (bdt(2)(-), E(1/2)(Pd(III)/Pd(II)) = 0.22 V; tdt(2)(-), E(1/2)(Pt(III)/Pt(II)) = 0.20 V; dmid(2)(-), E(1/2)(Pd(III)/Pd(II)) = 0.19 V; dmit(2)(-), E(1/2)(Pt(III)/Pt(II)) = 0.19 V) but not for the relatively electron-poor dithiolene, maleonitriledithiolate (mnt(2)(-)). The X-ray structure of Ni[pz(NMe(2))(2)(Pr)(6)]Pd(mnt) (13) was determined. Crystal data for C(85)H(109)Cl(3)N(24)Ni(2)Pd(2)S(4): space group P2(1)/n; a = 17.435(4) Å, b = 17.982(2) Å, c = 30.577(2) Å; beta = 104.27(2) degrees; Z = 4.
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