Dihydrogen complexes of iridium and rhodium

Michael Findlater, Katherine M. Schultz, Wesley H. Bernskoetter, Alison Cartwright-Sykes, D. Michael Heinekey, Maurice Brookhart

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56 Scopus citations


A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)Ir(H)(H 2)] [BAr f 4] (1-H 3), (POCOP)Rh(H 2) (2-H 2), [(PONOP)Ir(C 2H 4)] [BAr f 4] (3-C 2H 4), [(PONOP)Ir(H) 2)] [BAr f 4] (3-H 2), [(PONOP)Rh(C 2H 4)] [BAr f 4] (4-C 2H 4) and [(PONOP)Rh(H 2)] [BAr f 4] (4-H 2) (POCOP = I 3-C 6H 3-2,6-[OP(tBu) 2] 2; PONOP = 2,6-(tBu 2PO) 2C 5H 3N; BAr f 4 = tetrakis(3,5-trifluoromethylphenyl)borate). The nature of the dihydrogen-metal interaction was probed using NMR spectroscopic studies. Complexes 1-H 3, 2-H 2, and 4-H 2 retain the H-H bond and are classified as η 2-dihydrogen adducts. In contrast, complex 3-H 2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T 1 and 1J HD coupling values: T 1 = 14 ms, 1J HD = 33 Hz for the dihydrogen ligand in 1-H 3, T 1(min) = 23 ms, 1J HD = 32 Hz for 2-H 2, T 1(min) = 873 ms for 3-H 2, T 1(min) = 33 ms, 1J HD = 30.1 Hz for 4-H 2.

Original languageEnglish
Pages (from-to)4672-4678
Number of pages7
JournalInorganic Chemistry
Issue number8
StatePublished - Apr 16 2012


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