TY - JOUR
T1 - Reactivities of π-electron-rich phosphorus-nitrogen ligands toward Groups VIB and VIIB metal carbonyl complexes
AU - WONG, Wai Yeung
AU - WONG, Rick W K
AU - Sun, Chaode
AU - Wong, Wing Tak
N1 - Funding Information:
W.-K. Wong and W.-Y. Wong thank the Hong Kong Baptist University and the Hong Kong Research Grants Council for financial support. W.-T. Wong thanks the Hong Kong Research Grants Council and the University of Hong Kong for financial support.
PY - 2000/10/20
Y1 - 2000/10/20
N2 - The interaction of (Ph2PN=)C(Ph)[N(SiMe3)2] (L1) with one equivalent of Mn(CO)5Br afforded cis-Mn(CO)4Br-{(Ph2PN=)C(Ph)[N(SiMe3) 2]} (1), which upon boiling in THF gave fac-Mn(CO)3Br[(Ph2PNH)C(Ph)(=NSiMe3)] (2), and with one equivalent of Re(CO)5X (X = Br or Cl) gave fac-Re(CO)3X[(Ph2PNH)C(Ph)(=NH)] [X = Br (3) or Cl (4)] in good yield. Reaction of 1,4-C6H4{C(=NPPh2)[N(SiMe3) 2]}2 (L2) with two equivalents of Mn(CO)5Br gave the symmetric dimer [cis-Mn(CO)4Br]2 {(Ph2PN=)[N(SiMe3)2]C}2C 6H4-1,4 (5), and with two equivalents of Re(CO)5Br gave the cyclic dimer cyclo-[fac-(Me2NCHO)Re(CO)3(μ-Ph2PO 2)]2 (6) upon recrystallization in DMF. Treatment of (NC5H4){(Ph2PN=)C[N(SiMe3) 2]}-4 (L3) with one equivalent of (nbd)M(CO)4 (M = Mo or Cr, nbd = norbornadiene) in THF produced cis-M(CO)4{(NC5H4)-[(Ph 2PNH)C(=NSiMe3)]-4} [M = Mo (7) or Cr (8)], and with excess Mn(CO)5Br led to the trinuclear complex fac-{cis-Mn(CO)4Br[(NC5H4){(Ph 2PN=)C[N(SiMe3)2]}-4]}2Mn(CO) 3Br (9) in good yield. Compound 7, in the presence of CdCl2, hydrolyzed to cis-Mo(CO)4{(NC5H4)[(Ph 2PNH)C(=NH)]-4} (10). Compound 8 reacted with half an equivalent of Mn(CO)5Br to give the trinuclear complex fac-[cis-Cr(CO)4{(NC5H4)[(Ph 2PNH)C(=NSiMe3)]-4}]2Mn(CO)3Br (11). All the new compounds were characterized by spectroscopic and analytical methods and the structures of compounds 1, 3, 6, 9 and 10 were established by X-ray crystallography.
AB - The interaction of (Ph2PN=)C(Ph)[N(SiMe3)2] (L1) with one equivalent of Mn(CO)5Br afforded cis-Mn(CO)4Br-{(Ph2PN=)C(Ph)[N(SiMe3) 2]} (1), which upon boiling in THF gave fac-Mn(CO)3Br[(Ph2PNH)C(Ph)(=NSiMe3)] (2), and with one equivalent of Re(CO)5X (X = Br or Cl) gave fac-Re(CO)3X[(Ph2PNH)C(Ph)(=NH)] [X = Br (3) or Cl (4)] in good yield. Reaction of 1,4-C6H4{C(=NPPh2)[N(SiMe3) 2]}2 (L2) with two equivalents of Mn(CO)5Br gave the symmetric dimer [cis-Mn(CO)4Br]2 {(Ph2PN=)[N(SiMe3)2]C}2C 6H4-1,4 (5), and with two equivalents of Re(CO)5Br gave the cyclic dimer cyclo-[fac-(Me2NCHO)Re(CO)3(μ-Ph2PO 2)]2 (6) upon recrystallization in DMF. Treatment of (NC5H4){(Ph2PN=)C[N(SiMe3) 2]}-4 (L3) with one equivalent of (nbd)M(CO)4 (M = Mo or Cr, nbd = norbornadiene) in THF produced cis-M(CO)4{(NC5H4)-[(Ph 2PNH)C(=NSiMe3)]-4} [M = Mo (7) or Cr (8)], and with excess Mn(CO)5Br led to the trinuclear complex fac-{cis-Mn(CO)4Br[(NC5H4){(Ph 2PN=)C[N(SiMe3)2]}-4]}2Mn(CO) 3Br (9) in good yield. Compound 7, in the presence of CdCl2, hydrolyzed to cis-Mo(CO)4{(NC5H4)[(Ph 2PNH)C(=NH)]-4} (10). Compound 8 reacted with half an equivalent of Mn(CO)5Br to give the trinuclear complex fac-[cis-Cr(CO)4{(NC5H4)[(Ph 2PNH)C(=NSiMe3)]-4}]2Mn(CO)3Br (11). All the new compounds were characterized by spectroscopic and analytical methods and the structures of compounds 1, 3, 6, 9 and 10 were established by X-ray crystallography.
KW - Carbonyl
KW - Chromium
KW - Manganese
KW - Molybdenum
KW - Rhenium
UR - http://www.scopus.com/inward/record.url?scp=0347934704&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(00)00475-7
DO - 10.1016/S0022-328X(00)00475-7
M3 - Journal article
AN - SCOPUS:0347934704
SN - 0022-328X
VL - 612
SP - 160
EP - 171
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -