Tuesday, June 10, 2014

Gas-Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes

Womack, C. C.; Crabtree, K. N.; McCaslin, L.; Martinez, O.; Field, R. W.; Stanton, J. F.; McCarthy, M. C.  Angew. Chem. Int. Ed. 2014, 53, 4089
Contributed by Steven Bachrach.
Reposted from Computational Organic Chemistry with permission

Dihdroxycarbene was the subject of a post a few years ago relating to how this carbene does not undergo tunneling,1 while related hydroxycarbene do undergo a tunneling rearrangement.

Now we have a gas-phase microwave determination of the trans,cis isomer of dihydroxycarbene.2 The computed CCSD(T)/cc-pCVQZ structure is shown in Figure 1. What is truly remarkable here is the amazing agreement between the experimental and computed structure – as seen in Table 1.The bond distance are in agreement within 0.001 Å and the bond angles agree within 0.3°! Just further evidence of the quality one can expect from high-level computations. And computing this structure was certainly far easier than the experiments!

Figure 1. CCSD(T)/cc-pCVQZ optimized geometry of dihydroxycarbene.

Table 1. Experimental and computed (CCSD(T)/cc-pCVQZ) geometric parameters of dihydroxycarbene.a


Expt.
Comp.
C-O
1.335
1.336
C-O
1.309
1.309
O-Htrans
0.961
0.960
O-Hcis
0.976
0.975
O-C-O
107.30
107.25
C-O-H­­trans
106.8
106.8
C-O-H­­cis
110.7
110.4

aDistances in Å and angles in deg.


References

(1) Schreiner, P. R.; Reisenauer, H. P. "Spectroscopic Identification of Dihydroxycarbene," Angew. Chem. Int. Ed. 200847, 7071-7074, DOI: 10.1002/anie.200802105.
(2) Womack, C. C.; Crabtree, K. N.; McCaslin, L.; Martinez, O.; Field, R. W.; Stanton, J. F.; McCarthy, M. C. "Gas-Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes,"Angew. Chem. Int. Ed. 201453, 4089-4092, DOI: 10.1002/anie.201311082.


InChIs

Dihydroxycarbene: InChI=1S/CH2O2/c2-1-3/h2-3H
InChIKey=VZOMUUKAVRPMBY-UHFFFAOYSA-N



This work is licensed under a Creative Commons Attribution-NoDerivs 3.0 Unported License.