Syntheses and characterization of dichlorozirconium porphyrin complexes and their novel organometallic derivatives. X-ray structure of Zr(TPP)Cl[sub 2](THF)

Journal Article · Wed Feb 03 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

OSTI ID:7070470

Kim, Heejoon; Whang, Dongmok; Kim, Kimoon ^[1]; Do, Youngkyu ^[2]

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1. Pohang Inst. of Science and Technology (Korea, Republic of)
2. Korea Advanced Inst. of Science and Technology, Taejon (Korea, Republic of)

The chemistry of early transition metal porphyrin complexes, especially, that of the second- and third-row metal complexes has not been developed much due in part to their high oxophilicity. The authors have been interested in exploring zirconium and hafnium porphyrin complexes because they may show a rich organometallic chemistry as zirconocene derivatives do. The key entry to the organometallic zirconium porphyrin complexes would be Zr(porphyrin)Cl[sub 2], analogous to ZrCp[sub 2]Cl[sub 2]. The dichloride complex may be converted to organometallic [sigma]-complexes such as dialkyl complexes by the reactions with alkyllithium or Grignard reagents. It may also form organometallic [tau]-complexes by replacing the two chlorides with a cyclooctatetraenyl dianion or a dicarbollide dianion. Indeed, the authors have succeeded in preparing Zr(por)Cl[sub 2] (por = OEP, TPP) and their organometallic derivatives Zr(TPP)Me[sub 2] and Zr(OEP)([eta][sup 5]-C[sub 2]B[sub 9]H[sub 11]). They have presented the preliminary results on their syntheses and characterization by spectroscopy but have been unable to grow X-ray-quality crystals of either of the organometallic complexes until recently. When they finished the structural characterization of Zr(OEP)([eta][sup 5]C[sub 2]B[sub 9]H[sub 11]) by X-ray crystallography, however, Arnold and co-workers published the synthesis and characterization of Zr(OEP)Cl[sub 2] and several organometallic complexes derived from it, including Zr(OEP)(CH[sub 2]SiMe[sub 3])[sub 2] and Zr(OEP)([eta][sup 5]-C[sub 2]B[sub 9]H[sub 11]). Here they present their results on the syntheses and characterization of Zr(por)Cl[sub 2] (por = OEP, TPP), Zr(TPP)Me[sub 2], and Zr(OEP)([eta][sup 5]-C[sub 2]B[sub 9]H[sub 11]) and the X-ray structure of Zr(TPP)Cl[sub 2](THF). 22 refs., 2 tabs.

• OSTI ID: 7070470
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:3; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ZIRCONIUM CHLORIDES
MOLECULAR STRUCTURE
ZIRCONIUM COMPLEXES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
LATTICE PARAMETERS
ORGANOMETALLIC COMPOUNDS
PORPHYRINS
X-RAY DIFFRACTION
CARBOXYLIC ACIDS
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
ZIRCONIUM COMPOUNDS
400201* - Chemical & Physicochemical Properties