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Solid Rh crystals isomerize butene without dissolving
A crystalline Rh σ-alkane complex swaps NBA for alkenes in the solid state and the porous ethene polymorph isomerizes 1-butene with high TOF.
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What is a SMOM-Cat?
A crystalline molecular organometallic that catalyzes solid/gas reactions.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
What role does the NBA ligand play?
A weakly bound token ligand that can be substituted by ethene, propene or 1-butene.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
Is ethene substitution SC-SC?
Yes—X-ray at 150 K shows the bis-ethene cation in an octahedron of [BArF4]–.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
What is the Hex polymorph’s porosity?
~1 nm pores and 25% solvent-accessible volume.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
How do Hex vs Oct TOFs compare for 1-butene?
Hex TOF(90%) = 1160 h–1 vs 29 and 20 h–1 for NBA and Oct.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
What 31P SSNMR shift marks the bis-ethene complex?
δ 73.7, 36 ppm upfield of [1-NBA][BArF4].
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
How stable is the ethene complex in solution?
Significant decomposition after 20 min at 298 K in CD2Cl2.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
What barrier was fitted for propene fluxionality?
ΔG‡ = 10(1) kcal mol–1 from 31P lineshape.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
Is the η2-propene or allyl-hydride lower in the lattice?
η2-propene/γ-agostic lies 3.4 kcal mol–1 below the allyl hydride.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
Why do CF3 groups help SC-SC chemistry?
They add lattice plasticity so NBA can leave despite few channels.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified
What 13C SSNMR signal is assigned to bound ethene?
A broad peak at δ 82.3.
Source: Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates · DOI · quote verified