Octacoordinate metal carbonyls of scandium and yttrium: theoretical calculations and experimental observation

Abstract

Comparisons between the theoretical calculations and the experimental observations indicate that eight CO ligands are chemically bonded on the central atom in the singlet state of Sc(CO)8(+) ((1)A1 state of D(4d) symmetry) and the singlet and triplet states of Y(CO)8(+) ((1)A1 state of D(4d) symmetry and (3)A(1g) state of O(h) symmetry). The (1)A1 states of both Sc(CO)8(+) and Y(CO)8(+) have the 18-electron d(10)s(2)p(6) noble gas configuration. In M(CO)9(+) (M = Sc or Y), the ninth CO is weakly adsorbed on the external shell.

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013

“…A reaction of the scorpionateanchored yttrium-dibenzyl complex Tp Me2 Y(CH 2 Ph) 2 (THF) (Tp Me2 = tris (3,5-dimethylpyrazolyl)borate) with phenyl isothiocyanate led to C S bond cleavage to give a cubane-type yttrium-sulfur cluster, [Tp Me2 Y( 3 -S)] 4 , accompanied by the elimination of PhN C(CH 2 Ph) 2 as illustrated in Scheme 12. However, Tp Me2 Y(CH 2 Ph) 2 (THF) reacted with phenyl isocyanate to afford a C(sp 3 [10].…”

“…The 1 A 1 states of both Sc(CO) 8 + and Y(CO) 8 + have the 18-electron d 10 s 2 p 6 noble gas configuration. In M(CO) 9 + (M = Sc, Y), the ninth CO is weakly adsorbed on the external shell [4]. Divalent ytterbium compounds containing the tris(dimethylsilyl)methyl ligand have been described.…”

“…It was found that dinitrogen can be reduced by photochemical activation of the Ln 3+ mixed-ligand tris(cyclopentadienyl) 4 ], which was then allowed to react with KCp to produce Cp 3 Lu as a yellow microcrystalline solid in good yield (86%) (Scheme 84) [60].…”

“…The synthesis begins with the preparation of the colorless cerium(III)-methanide Ce(BIPM TMS H)I 2 (THF) from CeI 3 (THF) 4 and Rb(BIPM TMS H) (89% yield), followed by treatment with benzylpotassium to afford the cerium(III)-carbene Ce(BIPM TMS )I(DME) as a colorless powder (72% yield). Treatment of Ce(BIPM TMS )I(DME) with one equivalent of K(ODipp) (Dipp = 2,6-diisopropylphenyl) affords the yellow cerium(III) carbene aryloxide Ce(BIPM TMS )(ODipp)(THF) (35% yield), which when treated with a further equivalent of K(ODipp) afforded the "ate" cerium(III) carbene bis(aryloxide) [Ce(BIPM TMS )(ODipp) 2 be prepared directly from Ce(BIPM TMS )I(DME) and two equivalents of K(ODipp), because it was found that Ce(BIPM TMS )(ODipp)(THF) is unstable in solution and decomposes surprisingly easily.…”

“…In addition, the studied Sc(CO) n complexes generally favor the low-spin ground state (doublet) structures except ScCO and Sc(CO) 3 that are in the quartet states. The previously uncertain spectrum bands were assigned to Sc(CO) 4 and Sc(CO) 5 in this work. In all, the appreciable stability suggested that the 18-electron first-row transition metal carbonyls, i.e., Sc(CO) 7 − and Sc(CO) 6 3− could be accessible experimentally [3].…”