Salt-free synthesis of samarium-aluminum mixed-metal alkoxides: X-ray crystal structures of [[(i-Pr-O)(i-Bu)Al(mu-O-i-Pr)(2)Sm(O-i-Pr)(HO-i-Pr)](mu-O-i-Pr)](2), [(THF)(2)Sm(O-t-Bu)(2)(mu-O-t-Bu)(2)Al(i-Bu)(2)], Sm(OAr)(3)(THF)(3) (Ar = 2,4,6-Me(3)C(6)H(2)), [Nd(mu-OAr)(OAr)(2)(py)(2)](2) (Ar = 2,4,6-Me(3)C(6)H(2)), and (ArO)(3)Sm[(mu-O-t-Bu)(2)Al(2)(O-t-Bu)(4)] (Ar = 2,6-i-Pr(2)C(6)H(3)).
Reaction of equimolar quantities of Sm[N(SiMe(3))(2)](3) and Al(i-Bu)(3) with 6 equiv of iso-propyl alcohol in toluene leads to the formation of the mixed-metal alkoxide complex [[(i-Pr-O)(i-Bu)Al(mu-O-i-Pr)(2)Sm(O-i-Pr)(HO-i-Pr)](mu-O-i-Pr)](2) (1). An analogous reaction between 1:1 Sm[N(SiMe(3))(2)](3)/Al(i-Bu)(3) and 6 equiv of tert-butyl alcohol, followed by addition of THF, produces the THF adduct [(THF)(2)Sm(O-t-Bu)(2)(mu-O-t-Bu)(2)Al(i-Bu)(2)] (2). Compound 1 crystallizes in the space group P1 while 2 crystallizes in space group Cmcm. Cell parameters for 1: a = 11.028(2) A, b = 12.168(2) A, c = 12.879(2) A, alpha = 82.84(1) degrees, beta = 64.88(1) degrees, gamma = 70.80(1) degrees, Z = 1. Cell parameters for 2: a = 11.304(2) A, b = 22.429(4) A, c = 15.768(2) A, Z = 4. Attempts to prepare the bulkier derivatives result in the formation of lanthanide aryloxide species only; reaction between equimolar amounts of Ln[N(SiMe(3))(2)](3) (Ln = Sm, Nd) and Al(i-Bu)(3) with 6 equiv of HO-2,4,6-Me(3)C(6)H(2), followed by the addition of THF or pyridine, yields the Lewis base adducts Sm(OAr)(3)(THF)(3) (3) and [Nd(mu-OAr)(OAr)(2)(py)(2)](2) (4). Compound 3 crystallizes in the space group Pbca while 4 crystallizes in space group P2(1)/c. Cell parameters for 3: a = 16.5822(9) A, b = 15.5668(9) A, c = 29.902(2) A, Z = 8. Cell parameters for 4: a = 13.4496(8) A, b = 20.034(1) A, c = 16.206(1) A, beta = 113.782(1) degrees, Z = 2. Reaction of Al(2)(O-t-Bu)(6) with [Sm(OAr)(3)](2) (Ar = 2,6-i-Pr(2)C(6)H(3)) yields the adduct (ArO)(3)Sm[(mu-O-t-Bu)(2)Al(2)(O-t-Bu)(4)] (5), which crystallizes in the space group P2(1)/n. Cell parameters for 5: a = 14.0960(7) A, b = 27.3037(15) A, c = 16.7893(9) A, beta = 92.216(1) degrees, Z = 4.
Giesbrecht
Garth R
GR
Nuclear Materials Technology (NMT) Division, Chemistry (C) Division, and the Glenn T. Seaborg Institute for Transactinium Science, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
Gordon
John C
JC
Clark
David L
DL
Scott
Brian L
BL
Watkin
John G
JG
Young
Kenneth J
KJ