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Isolating rare arylhalodiphosphene P=P–X bonds
A bulky aryl-PPCl diphosphene is isolated as a monomer, swapped to Br and I, and shown to have a P=P double bond unlike diazonium chlorides.
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What compound is the headline isolation?
8·(Et2O)2, a thermally robust monomeric arylhalodiphosphene.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
What 31P NMR pattern indicates P=P in 8?
Downfield signals at 433 and 502 ppm with 1JPP = 574 Hz.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
What E/Z occupancies are in the crystal of 8?
85% E and 15% Z.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
How is the P–Cl bond used synthetically?
Halogen exchange with TMSBr and TMSI gives 9 and 10.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
What happens with GaCl3 or AlCl3?
Rapid decomposition to complex mixtures.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
What does AgOTf do instead?
Forms coordination complex 11.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
How much more stable is E-8* than Z-8* by DFT?
2.96 kcal mol−1 more favorable enthalpy.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
How does bonding in 8 differ from aryldiazonium chlorides?
It has a formal P=P double bond and a covalent P–Cl single bond, not an ion pair.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
At what temperature does TMSX exchange occur?
16 h at 100 °C in toluene; not at 0 °C or room temperature.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
What DFT level was used for the model diphosphenes?
PBE0-D3/def2-TZVPP.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified
What happens to the P–P bond with aqueous HBr?
Protonolysis cleaves it to give compound 4.
Source: Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond, length as m-dash]P-X bonding (X = Cl, Br, I) · DOI · quote verified