Synthesis, structure, and reactivity of zirconium and hafnium imido metalloporphyrins

Joseph L. Thorman, Ilia A. Guzei, Victor G. Young, L. Keith Woo

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The zirconium and hafnium porphyrin imido complexes (TTP)M=NAriPr [TTP = meso-tetra-p-tolylporphyrinato dianion, M = Zr (1), Hf (2), AriPr = 2,6-diisopropylphenyl] were synthesized from (TTP)MCl2 and 2 equiv of LiNHAriPr. The zirconium imido complex, (TTP)Zr=NAriPr, was also obtained from the preformed imido complex Zr(NAriPr)Cl2(THF)2 and (TTP)Li2(THF)2. Treatment of (TTP)HfCl2 with excess LiNH(p-MeC6H4) resulted in the formation of a bis(amido) complex, (TTP)Hf(NH-p-MeC6H4)2 (3), instead of an imido complex. In the presence of excess aniline, 2 formed an equilibrium mixture of bis(amido) compounds, (TTP)Hf(NHPh)(NHAriPr) and (TTP)Hf(NHPh)2. The nucleophilic character of the imido moiety is exhibited by its reaction with 1BuNCO, producing isolable N,O-bound ureato metallacycles. The kinetic product obtained with zirconium, (TTP)Zr(η2-NAriPrC(=NtBu)O) (4a), isomerized to (TTP)Zr(η2-NtBuC(=NAriPr)O) (4b) in solution. Upon being heated to 80 °C, 4a produced the carbodiimide AriPrN=C=NtBu and a transient Zr(IV) oxo complex. The analogous hafnium complex (TTP)Hf(η2-NAriPrC(=NtBu)O) (5a) did not eject the carbodiimide upon heating to 110 °C but isomerized to (TTP)Hf(η2-NtBuC(=NAriPr)O) (5b). To support the formulation of 4a and 5a as N,O bound, the complex (TTP)Hf(η2-NAriPrC(=NAriPr)O) (6) was studied by variable-temperature NMR spectroscopy. The corresponding thio- and selenoureato metallacycles were not isolable in the reaction between 1 and 2 with tBuNCS and tBuNCSe. Concomitant formation of the metallacycle with decomposition to the carbodiimide, AriPrN=C=NtBu, reflects the lower C-Ch bond strength in the proposed N,Ch-bound metallacycles. Treatment of 2 with 1,3-diisopropylcarbodiimide resulted in the η2-guanidino complex (TTP)Hf(η2-NAriPrC(=NiPr)NiPr) (7a), which isomerized to the less sterically crowded isomer (TTP)Hf(η2-NiPrC(=NAriPr)NiPr) (7b). Complexes 1, 2, 4a, 4b, and 7a were characterized by X-ray crystallography. The monomeric terminal imido compounds, 1 and 2, are isomorphous: M-Nimido distances of 1.863(2) Å (Zr) and 1.859(2) Å (Hf); M-Nimido-C angles of 172.5(2)° (Zr) and 173.4(2)° (Hf). The structures of the ureato complexes 4a and 4b and the guanidino complex 7a exhibit typical alkoxido and amido bond distances (Zr-N = 2.1096(13) Å (4a), 2.137(3) Å (4b); Zr-O = 2.0677(12) Å (4a), 2.066(3) Å (4b); Hf-N = 2.087(2) Å, 2.151(2) Å (7a)).

Original languageEnglish (US)
Pages (from-to)3814-3824
Number of pages11
JournalInorganic chemistry
Issue number17
StatePublished - 1999


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