TY - JOUR
T1 - Dihydrogen complexes of iridium and rhodium
AU - Findlater, Michael
AU - Schultz, Katherine M.
AU - Bernskoetter, Wesley H.
AU - Cartwright-Sykes, Alison
AU - Heinekey, D. Michael
AU - Brookhart, Maurice
PY - 2012/4/16
Y1 - 2012/4/16
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84859788613&partnerID=8YFLogxK
U2 - 10.1021/ic202630x
DO - 10.1021/ic202630x
M3 - Article
C2 - 22364621
AN - SCOPUS:84859788613
SN - 0020-1669
VL - 51
SP - 4672
EP - 4678
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 8
ER -