Carbon dioxide insertion processes involving metal-carbon bonds: solid-state and solution structure of (18-crown-6) sodium pentacarbonylmethyltungstate(1-)

New Forms of Coordinated Carbon: Wirelike Cumulenic C3 and C5 sp Carbon Chains that Span Two Different Transition Metals and Mediate Charge Transfer

“…The rhenium−carbon bond length (1.973(7) Å) is between those in two redox-related complexes derived from VI -Me 5 with ReC⋮CC⋮CRe and + ReCCCCRe + linkages (2.037(5), 1.93(1)−1.91(1) Å). 6a, The Re C ≡ C bond length (1.23(1) Å) is close to the mean for alkynyl complexes (1.210(13) Å), but the ReC⋮ CC  bond length (1.38(1) Å) is short for sp−sp 2 junctions (1.43 Å) 23b than anionic alkyl complexes ([RW(CO) 5 ] - , 2.31−2.34 Å). ,

2 Views of the molecular structure of 3 (top) and Newman-type projection down the C42−Re linkage (bottom).

1 Summary of Crystallographic Data for (η 5 -C 5 Me 5 )Re(NO)(PPh 3 )(C⋮CC(OMe))W(CO) 5 ( 3 ) and [(η 5 -C 5 Me 5 )Re(NO)(PPh 3 )(CCC)Mn(CO) 2 (η 5 -C 5 H 5 )] + BF 4 - ·(CH 2 Cl 2 ) 0.5 ( 9 ·(CH 2 Cl 2 ) 0.5 ) 3 9 ·(CH 2 Cl 2 ) 0.5 formula C 37 H 33 NO 7 PReW C 77 H 72 B 2 Cl 2 F 8 N 2 Mn 2 - O 6 P 2 Re 2 a formula weight 1004.702 1910.18 crystal system triclinic triclinic space group P 1̄ P 1̄ cell dimensions a , Å 13.125(2) 8.732(1) b , Å 13.837(3) 15.248(4) c , Å 10.880(2) 28.850(5) α, deg 109.16(2) 84.68(2) β, deg 92.48(2) 97.01(1) γ, deg 77.80(2) 102.40(2) V, Å 3 1823.55 3714.80 Z 2 2 temp of collection (°C) 16 −125 d calc , g/cm 3 1.8301.71 d found , g/cm 3 (22 °C) 1.805 1.701 reflections measured 6765 12 998 total unique data 6394 12 051 observed data, I > 3σ( I ) 5207 8935 no. of variables 433 928 goodness of fit 0.90 2.04 R = ∑|| F o | − | F c ||/∑| F o | 0.029 0.054 R w = ∑|| F o | − | F c || w 1/2 /∑| F o | w 1/...…”

Polymetallated 4‐tert‐Butylcalix[4]arene Complexes of Sodium and Potassium Stabilized by Crown Ethers: Syntheses, Structures and Activation of Carbon Dioxide

“…Furthermore, the coordinated THF and the oxygen of the phenolate group lie trans to each other, perpendicular to the plane formed by the crown ether. This type of coordination is, in principle, well‐known for symmetric 18‐crown‐6 sodium complexes of the type [(18‐crown‐6)NaL 2 ]X (L = THF,27−30 H 2 O31,32 with different anions; for a review see ref 33…”

“…The structural motif of the other cation [(dmf) 2 Na + (18‐crown‐6)] is typical of the above‐mentioned group of symmetrical [(18‐crown‐6)NaL 2 ] + complexes,27−33 with a hexagonal‐bipyramidal arrangement of the eight oxygen ligands surrounding the sodium ion. The sodium ion is situated in the center of the plane formed by the six oxygens of the crown ether compound.…”

Impacts of Oxo Interactions on Np(V) Crown Ether Complexes

“…Presence of hydronium in (H 3 O)­[K­(H 2 O) 3 ­(18-crown-6)]­Cl 2 ·H 2 O also results in buckling of the crown ether to create a distorted C 1 conformation. Similarly, the 18-crown-6 molecule in [Na­(THF) 2 ­(18-crown-6)]­[CH 3 W­(CO) 5 ] (THF = tetrahydrofuran) exhibits a planar arrangement about the equatorial plane, but the slight size mismatch between the cationic radii and the ligand often results in lower symmetry conformations. , …”

“…Similarly, the 18-crown-6 molecule in [Na-(THF) 2 (18-crown-6)][CH 3 W(CO) 5 ] (THF = tetrahydrofuran) exhibits a planar arrangement about the equatorial plane, but the slight size mismatch between the cationic radii and the ligand often results in lower symmetry conformations. 37,46 Crown Ether Complexes with Neptunyl−Cation (Na− Np) and Neptunyl−Neptunyl (Np−Np) Interactions. Addition of sodium cations to the neptunyl crown ether system led to the formation of isolated molecular complexes that exhibit neptunyl−cation interactions (Figure 3).…”