Synthesis and Characterization of Dihalogenoruthenium(IV)-, Diphenylruthenium(IV)-, and Phenylruthenium(III)-Tetraphenylporphyrin Complexes, Including the Crystal Structure of Ru(TPP)Br2

Mingzhe Ke; Chand Sishta; Brian R. James; David Dolphin; John W. Sparapany; James A. Ibers

doi:10.1021/ic00025a017

Synthesis and Characterization of Dihalogenoruthenium(IV)-, Diphenylruthenium(IV)-, and Phenylruthenium(III)-Tetraphenylporphyrin Complexes, Including the Crystal Structure of Ru(TPP)Br₂

Mingzhe Ke, Chand Sishta, Brian R. James^*, David Dolphin, John W. Sparapany, James A. Ibers

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

54 Scopus citations

Abstract

The paramagnetic (S=1) Ru(TPP)X₂ complexes (X = halide) are made by treatment of [Ru(TPP)]₂ with HBr, HC1, or I₂ (TPP = the dianion of 5,10,15,20-tetraphenylporphyrin). The dibromo species (2) crystallizes in the tetragonal system, space group [formula omitted with a = 13.686 (9) Å, c = 9.711 (7) Å, and Z = 2. The structure has been refined on F² to final R and R_w values of 0.050 and 0.080, respectively, for 72 variables and 1639 observations; the value of R(F) for the 1354 reflections having F_o² ≥ 3σ(F₀²) is 0.034. The molecule has imposed symmetry 4/m. As a consequence, the porphyrin plane is strictly planar; the phenyl rings are perpendicular to this plane, as is the Ru-Br bond. The Ru-Br distance is 2.425 (2) Å, the shortest recorded for any Ru-Br bond. ¹H NMR isotropic shift data are consistent with π-donation from the halide. With PhLi, 2 yields diamagnetic Ru(TPP)Ph₂ (5), which can be thermally decomposed to Ru(TPP)Ph (6); kinetic data imply a stronger Ru-C bond in 5 compared to the corresponding octaethylporphyrin complex (by 2.6 kcal/mol). A light-induced O₂ oxidation of 6 gives diamagnetic [Ru(TPP)Ph]₂O.

Original language	English (US)
Pages (from-to)	4766-4771
Number of pages	6
Journal	Inorganic chemistry
Volume	30
Issue number	25
DOIs	https://doi.org/10.1021/ic00025a017
State	Published - Dec 1 1991

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic00025a017

Cite this

@article{f7b75ab3c9af4bffbcab127f06df3c5d,

title = "Synthesis and Characterization of Dihalogenoruthenium(IV)-, Diphenylruthenium(IV)-, and Phenylruthenium(III)-Tetraphenylporphyrin Complexes, Including the Crystal Structure of Ru(TPP)Br2",

abstract = "The paramagnetic (S=1) Ru(TPP)X2 complexes (X = halide) are made by treatment of [Ru(TPP)]2 with HBr, HC1, or I2 (TPP = the dianion of 5,10,15,20-tetraphenylporphyrin). The dibromo species (2) crystallizes in the tetragonal system, space group [formula omitted with a = 13.686 (9) {\AA}, c = 9.711 (7) {\AA}, and Z = 2. The structure has been refined on F2 to final R and Rw values of 0.050 and 0.080, respectively, for 72 variables and 1639 observations; the value of R(F) for the 1354 reflections having Fo2 ≥ 3σ(F02) is 0.034. The molecule has imposed symmetry 4/m. As a consequence, the porphyrin plane is strictly planar; the phenyl rings are perpendicular to this plane, as is the Ru-Br bond. The Ru-Br distance is 2.425 (2) {\AA}, the shortest recorded for any Ru-Br bond. 1H NMR isotropic shift data are consistent with π-donation from the halide. With PhLi, 2 yields diamagnetic Ru(TPP)Ph2 (5), which can be thermally decomposed to Ru(TPP)Ph (6); kinetic data imply a stronger Ru-C bond in 5 compared to the corresponding octaethylporphyrin complex (by 2.6 kcal/mol). A light-induced O2 oxidation of 6 gives diamagnetic [Ru(TPP)Ph]2O.",

author = "Mingzhe Ke and Chand Sishta and James, {Brian R.} and David Dolphin and Sparapany, {John W.} and Ibers, {James A.}",

year = "1991",

month = dec,

day = "1",

doi = "10.1021/ic00025a017",

language = "English (US)",

volume = "30",

pages = "4766--4771",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "25",

}

Synthesis and Characterization of Dihalogenoruthenium(IV)-, Diphenylruthenium(IV)-, and Phenylruthenium(III)-Tetraphenylporphyrin Complexes, Including the Crystal Structure of Ru(TPP)Br₂. / Ke, Mingzhe; Sishta, Chand; James, Brian R. et al.
In: Inorganic chemistry, Vol. 30, No. 25, 01.12.1991, p. 4766-4771.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis and Characterization of Dihalogenoruthenium(IV)-, Diphenylruthenium(IV)-, and Phenylruthenium(III)-Tetraphenylporphyrin Complexes, Including the Crystal Structure of Ru(TPP)Br2

AU - Ke, Mingzhe

AU - Sishta, Chand

AU - James, Brian R.

AU - Dolphin, David

AU - Sparapany, John W.

AU - Ibers, James A.

PY - 1991/12/1

Y1 - 1991/12/1

N2 - The paramagnetic (S=1) Ru(TPP)X2 complexes (X = halide) are made by treatment of [Ru(TPP)]2 with HBr, HC1, or I2 (TPP = the dianion of 5,10,15,20-tetraphenylporphyrin). The dibromo species (2) crystallizes in the tetragonal system, space group [formula omitted with a = 13.686 (9) Å, c = 9.711 (7) Å, and Z = 2. The structure has been refined on F2 to final R and Rw values of 0.050 and 0.080, respectively, for 72 variables and 1639 observations; the value of R(F) for the 1354 reflections having Fo2 ≥ 3σ(F02) is 0.034. The molecule has imposed symmetry 4/m. As a consequence, the porphyrin plane is strictly planar; the phenyl rings are perpendicular to this plane, as is the Ru-Br bond. The Ru-Br distance is 2.425 (2) Å, the shortest recorded for any Ru-Br bond. 1H NMR isotropic shift data are consistent with π-donation from the halide. With PhLi, 2 yields diamagnetic Ru(TPP)Ph2 (5), which can be thermally decomposed to Ru(TPP)Ph (6); kinetic data imply a stronger Ru-C bond in 5 compared to the corresponding octaethylporphyrin complex (by 2.6 kcal/mol). A light-induced O2 oxidation of 6 gives diamagnetic [Ru(TPP)Ph]2O.

AB - The paramagnetic (S=1) Ru(TPP)X2 complexes (X = halide) are made by treatment of [Ru(TPP)]2 with HBr, HC1, or I2 (TPP = the dianion of 5,10,15,20-tetraphenylporphyrin). The dibromo species (2) crystallizes in the tetragonal system, space group [formula omitted with a = 13.686 (9) Å, c = 9.711 (7) Å, and Z = 2. The structure has been refined on F2 to final R and Rw values of 0.050 and 0.080, respectively, for 72 variables and 1639 observations; the value of R(F) for the 1354 reflections having Fo2 ≥ 3σ(F02) is 0.034. The molecule has imposed symmetry 4/m. As a consequence, the porphyrin plane is strictly planar; the phenyl rings are perpendicular to this plane, as is the Ru-Br bond. The Ru-Br distance is 2.425 (2) Å, the shortest recorded for any Ru-Br bond. 1H NMR isotropic shift data are consistent with π-donation from the halide. With PhLi, 2 yields diamagnetic Ru(TPP)Ph2 (5), which can be thermally decomposed to Ru(TPP)Ph (6); kinetic data imply a stronger Ru-C bond in 5 compared to the corresponding octaethylporphyrin complex (by 2.6 kcal/mol). A light-induced O2 oxidation of 6 gives diamagnetic [Ru(TPP)Ph]2O.

UR - http://www.scopus.com/inward/record.url?scp=33751498849&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33751498849&partnerID=8YFLogxK

U2 - 10.1021/ic00025a017

DO - 10.1021/ic00025a017

M3 - Article

AN - SCOPUS:33751498849

SN - 0020-1669

VL - 30

SP - 4766

EP - 4771

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 25

ER -

Synthesis and Characterization of Dihalogenoruthenium(IV)-, Diphenylruthenium(IV)-, and Phenylruthenium(III)-Tetraphenylporphyrin Complexes, Including the Crystal Structure of Ru(TPP)Br₂

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this