Metallcarbonyl-Komplexe mit Anionen von cyclischen Imiden / Metal Carbonyl Complexes with Anions of Cyclic Imides

Abstract

<jats:p>A large series of metal carbonyl complexes with N -bonded anions of various cyclic imidates (X<jats:sup>-</jats:sup>) has been prepared: [M(CO)<jats:sub>5</jats:sub>X]<jats:sup>-</jats:sup>, [M(CO)<jats:sub>4</jats:sub>(PPh<jats:sub>3</jats:sub>)X<jats:sup>]</jats:sup>, [M(CO)<jats:sub>3</jats:sub>(en)X]<jats:sup>-</jats:sup> (M = Cr, Mo, W), Re(CO)<jats:sub>5</jats:sub>X , [π-CH<jats:sub>3</jats:sub>C<jats:sub>5</jats:sub>H<jats:sub>4</jats:sub>Mn(CO)<jats:sub>2</jats:sub>X]<jats:sup>-</jats:sup>, [Mn(CO)<jats:sub>4</jats:sub>X<jats:sub>2</jats:sub>]<jats:sup>-</jats:sup>. Also pyromellitdiimidate and cyclopentanebis(dicarboximidate) bridged complexes [(OC)<jats:sub>5</jats:sub>MXM(CO)<jats:sub>5</jats:sub>]<jats:sup>2- </jats:sup>(M = Cr, Mo, W) and the dicyanamide complex [π-(C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>)Mn(CO)<jats:sub>2</jats:sub>NCNCN]<jats:sup>-</jats:sup> have been obtained. Reactions at the coordinated imidate ligands and the spectroscopic data of the complexes are reported.</jats:p>

Molybdenum Amido Complexes with Single MoN Bonds: Synthesis, Structure, and Reactivity

“…The IR spectrum of 7 in the ν CO region consists of the two expected cis ‐Mo(CO) 2 bands (at frequencies considerably higher than those of the amido precursor 2 b , reflecting the electron‐withdrawing ability of the carbonyl groups within the maleimide moiety), and a band at 1728 cm −1 due to the “organic” CO groups. In the 1 H NMR spectrum, the two olefinic hydrogen atoms are equivalent, in agreement with the symmetric structure (confirmed by its 13 C NMR spectrum, see Experimental Section) represented in Scheme , and in contrast with the ring‐opened product 6 described above 40. The MoN(amido) bond length in 7 (2.212(3) Å) is somewhat longer than that found in 2 b , reflecting the fact that the maleimidato ligand is a weaker donor than the p ‐tolyl group, as mentioned above with regard to the IR spectra.…”

Oxidative-addition of the N–H bond of saccharin (sacH) to a triosmium centre: Synthesis, structure and reactivity of Os3(CO)10(μ-H)(μ-sac)

“…The organometallic chemistry of the sac has been relatively neglected and only a few organometallic sac complexes are known [4][5][6][7][8]. In 1987, Beck and co-workers reported sac complexes of the Group VI metal carbonyls Na[M(CO)5(κ 1 -(N)-sac)] from the reactions of M(CO) 5(thf) and Na(sac) [8].…”

“…In 1987, Beck and co-workers reported sac complexes of the Group VI metal carbonyls Na[M(CO)5(κ 1 -(N)-sac)] from the reactions of M(CO) 5(thf) and Na(sac) [8]. More recently, Süss-Fink and co-workers reported a series of η 6 -arene complexes, (η 6 -arene)Ru(κ 1 -(N)-sac)2(L) (L = H2O, CH3CN), synthesized from [(η 6 -arene)RuCl2]2 and Na(sac) in a 1:1 mixture of water-ethanol or acetonitrile-methanol [7].…”

Synthesis and structure of rhenium carbonyl complexes bearing a saccharinate ligand

“…The saccharinate anion (sac), which readily forms due to the acidic nature of the lactam hydrogen, is soluble in water and can potentially provide four donor atoms for bonding with transition metal centers – one nitrogen and three oxygen (one ketonic and two sulfonic) [4] . As a result, the use of sac as a ligand auxiliary in various metal complexes remains under active investigation and has contributed to the growth of its coordination chemistry [4–13] . Simple N‐bound coordination ( I in Scheme 1) is the most commonly observed binding mode for the sac ligand, although it can coordinate with a transition metal in a number of different ways using the four donor atoms [4,5] …”

“…In contrast, the organometallic chemistry of sacH is still a developing area, and only a few organometallic sac complexes have been reported [6–13] . This prompted us to initiate a research program to investigate the reactivity of sacH and thiosaccharin (tsacH) with low‐valent metal carbonyl clusters [12–15] .…”