Etude comparative de l'alkylation des tetraphenylporphyrines de l'etain et de leurs formes reduites par les reactifs de grignard

Cloutour, Catherine; Debaig-Valade, Caroline; Gacherieu, Catherine; Pommier, Jean-Claude

doi:10.1016/0022-328x(84)80309-5

Cited by 11 publications

(7 citation statements)

References 7 publications

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“…Alkyllithium, aryllithium, or Grignard reagents are known to act as one-electron reducing reagents. [45][46][47][48][49] The reduction has been also demonstrated in several attempts to generate metalloporphyrins with metal-carbon bonds. 48,49 To clarify the point that the formation of (OTPP)Fe II (n-Bu) from (OTPP)Fe III Cl 2 has been preceded by one-electron reduction step, we have demonstrated that this species can be obtained by an independent route.…”

Section: Resultsmentioning

confidence: 99%

Iron Complexes of 5,10,15,20-Tetraphenyl-21-oxaporphyrin

Pawlicki

Latos‐Grażyński

2002

Inorg. Chem.

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The iron complexes of 5,10,15,20-tetraphenyl-21-oxaporphyrin (OTPP)H have been investigated. Insertion of iron(II) followed by one-electron oxidation yielded a high-spin, six-coordinate (OTPP)Fe(III)Cl(2) complex. The reduction of (OTPP)Fe(III)Cl(2) has been accomplished by means of moderate reducing reagents producing high-spin five-coordinate (OTPP)Fe(II)Cl. The molecular structure of (OTPP)Fe(III)Cl(2) has been determined by X-ray diffraction. The iron(III) 21-oxaporphyrin skeleton is essentially planar. The furan ring coordinates in the eta(1) fashion through the oxygen atom, which acquires trigonal geometry. The iron(III) apically coordinates two chloride ligands. Addition of potassium cyanide to a solution of (OTPP)Fe(III)Cl(2) in methanol-d(4) results in its conversion to a six-coordinate, low-spin complex [OTPP)Fe(III)(CN)(2)] which is spontaneously reduced to [OTPP)Fe(II)(CN)(2)](-) by excess cyanide. The spectroscopic features of [OTPP)Fe(III)(CN)(2)] correspond to the common low-spin iron(III) porphyrin (d(xy))(2)(d(xz)d(yz))(3) electronic configuration. Titration of (OTPP)Fe(III)Cl(2) or (OTPP)Fe(II)Cl with n-BuLi (toluene-d(8), 205 K) resulted in the formation of (OTPP)Fe(II)(CH(2)CH(2)CH(2)CH(3)). (OTPP)Fe(II)(n-Bu) decomposes via homolytic cleavage of the iron-carbon bond to produce (OTPP)Fe(I). The EPR spectrum (toluene-d(8), 77 K) is consistent with a (d(xy))(2)(d(xz))(2)(d(yz))(2)(d(z)(2)(1)(d[(x)(2)-(y)(2)])(0) ground electronic state of iron(I) oxaporphyrin (g(1) = 2.234, g(2) = 2.032, g(3) = 1.990). The (1)H NMR spectra of (OTPP)Fe(III)Cl(2), (OTPP)Fe(III)(CN)(2), ([(OTPP)Fe(III))](2)O)(2+), and (OTPP)Fe(II)Cl have been analyzed. There are considerable similarities in (1)H NMR properties within each iron(n) oxaporphyrin-iron(n) regular porphyrin or N-methylporphyrin pair (n = 2, 3). Contrary to this observation, the pattern of downfield positions of pyrrole resonances at 156.2, 126.5, 76.3 ppm and furan resonance at 161.4 ppm (273 K) detected for the two-electron reduction product of (OTPP)Fe(III)Cl(2) is unprecedented in the group of iron(I) porphyrins.

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Section: Resultsmentioning

confidence: 99%

Iron Complexes of 5,10,15,20-Tetraphenyl-21-oxaporphyrin

Pawlicki

Latos‐Grażyński

2002

Inorg. Chem.

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“…Three different methods have been reported for the synthesis of σ-bonded metalloporphyrins. The first involved a metathetical reaction of (por)MCl, (por)MCl 2 , or (por)M(OH) 2 with a carbanion source. ,,,, The second used oxidative addition of an alkyl or aryl halide to a low-valent metalloporphyrin complex. The third method employed a direct metalation of Li 2 (por) with an aryltin reagent, Ph 2 SnCl 2 …”

Section: Resultsmentioning

confidence: 99%

“…This is expected for an alkyl group σ-bonded to a main group metal of a metalloporphyrin, including the unstable (por)Sn(R) 2 (R = Et, Pr, i -Pr, Me 3 SiCH 2 , etc. ). , …”

Section: Resultsmentioning

confidence: 99%

Syntheses and Characterizations of Alkyl- and Amidotin Porphyrin Complexes: Molecular Structure oftrans-Bis(phenylacetylido)(meso-tetra-p-tolylporphyrinato)tin(IV)

Chen

Woo

1998

Inorg. Chem.

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Treatment of (TTP)SnCl 2 (TTP ) meso-tetra-p-tolylporphyrinato dianion) with an excess of lithium amides (LiNHPh, LiNPh 2 , o-C 6 H 4 (NHLi) 2 ) affords the metathesis products (TTP)Sn(NHPh) 2 (1), (TTP)Sn(NPh 2 ) 2 (2), and (TTP)Sn(o-C 6 H 4 (NH) 2 ) (3). Ligand exchanges of 1 with p-toluidine and 2,3,5,6-tetrafluoroaniline afford the complexes (TTP)Sn(p-NHC 6 H 4 Me) 2 (4) and (TTP)Sn(NHC 6 F 4 H) 2 (5), respectively. Treatment of (TTP)SnCl 2 with the bulky lithium (2,4,6-tri-tert-butylphenyl)amide or with PhNLiNLiPh does not form the corresponding amido or azobenzene complexes but produces the reduced product (TTP)Sn. In addition, the reaction of (TTP)-Sn(NHPh) 2 with PhHN-NHPh results in the production of (TTP)Sn, azobenzene, and aniline. The diethyl complex (TTP)SnEt 2 (6) can be prepared via the reaction of (TTP)SnCl 2 with 1 equiv of ZnEt 2 . The dineopentyl complex (TTP)Sn(CH 2 CMe 3 ) 2 (7) can be detected in the reaction of (TTP)SnCl 2 with neopentyllithium. The methyl derivatives cis-(TTP)SnMe 2 (8) and (TTP)SnMeBr (9) can be obtained by the treatment of (TTP)Li 2 (THF) 2 with 1 equiv of Me 2 SnBr 2 at low temperature in toluene and CH 2 Cl 2 , respectively. Treatment of (TTP)SnCl 2 with an excess of alkynyllithium salts (LiCtCPh, LiCtCSiMe 3 ) affords the metathesis products (TTP)Sn(CtCPh) 2 (10) and (TTP)Sn(CtCSiMe 3 ) 2 (11). Complexes 10 and 11 are inert at ambient temperature and are not photosensitive. Complex 10 reacts stepwise with excess MeOH cleanly to convert to (TTP)Sn(CtCPh)(OMe) (12) and then to (TTP)Sn(OMe) 2 (13) with increasing reaction time. The lability of the axial ligands in these tin porphyrin complexes correlates inversely with the basicity of the axial group. The crystal structure of 10 (monoclinic, P2 1 /c, a ) 10.9424(2) Å, b ) 14.5565(5) Å, c ) 16.4968(6) Å, R ) 90°, ) 100.7930(10) o , γ ) 90°, R 1 ) 3.53%, and wR 2 ) 8.90%) was determined from X-ray diffraction data.

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“…The alkylation of (P)Sn(OH)2 by Grignard reagents where P = TPP, TPC, or TPiBC gave (dialkylstannyl)isobacteriochlorins. 227 The presence of a transition-metal impurity in the Grignard reagent led to reduction of the macrocycle rather than toward tin alkylation of TPP and TPC.227 This suggests a oneelectron-transfer mechanism when the macrocycle is alkylated by Grignard reagents.…”

Section: Rhodium(ii) Complexesmentioning

confidence: 99%

“…TPP)Ge(R)2, where R = CH3, rc-C3H7, n-C8H17, and C6H5, were first synthesized from (TPP)GeCl2 as NMR shift reagents.220,221 Later, other (TPP)M(R)2 complexes were synthesized by treating (TPP)MC12 with RMgX, where M = Ge and R = C2H5, n-C3H7, n-C4H9, i-C4H9, CH2Si(CH3)3, CH2CH=CH2, or n-C6Hi3 or where M = Sn and R = C2H5 or CH^UCH^ 224,225,227. Most of these complexes have only been characterized in solution.…”

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confidence: 99%