Recombination of an Fe-Si-P Linkage to an Fe-P-Si Linkage through an Isolable Intermediate Phosphasilaferracyclopropane

Okazaki, M.; Yoshitomo, T.; Naito, J.; Sato, A.; Komuro, T.; Tobita, H. J. Am. Chem. Soc. 2008, 130, 17674-17675
h - CO Me2 Fe Si OC P Ph2 2 CO

Fe SiMe2 OC OC PPh2 1

Fe PPh OC OC SiMe2Ph 3

Peter H.M. Budzelaar

Fe OC PhP Si H Me2 4

Recombination ...
What happens ?
synthesis, characterization

How does it happen ?

mechanism

Why is it important ?
according to the authors

Evaluation

Fe-Si-P to Fe-P-Si

Synthesis and characterization

Complex 2 formed from 1 by irradiation in benzene
as reported previously

Now found not to be stable in the presence of CO

so if you do the synthesis, the CO released can react with 2

Procedure for synthesis of 3: Irradiate sample of 1, then let it sit in the dark for a while with added CO Characterization of 3: Xray, NMR
long Si-P bond, short (and strong) Fe-P bond

Fe SiMe2 OC OC PPh2 1

h - CO

Me2 Si Fe OC P Ph2 2

CO

Fe PPh OC OC SiMe2Ph 3
Fe-Si-P to Fe-P-Si

Synthesis and characterization

In the absence of CO, 2 also rearranges, but now to 4
characterized by NMR only a possible alternative structure is also mentioned (4', note 7) but considered less probable mixture of two isomers (1.7:1)

Me2 Si Fe OC P Ph2 2

Fe OC PhP Si H Me2 4

Me2 Fe Si OC P Ph H 4'

Fe-Si-P to Fe-P-Si

Synthesis and characterization

Complex 5, the cyclohexyl analogue of 2, is stable in both absence and presence of CO
characterized by Xray, NMR

Me2 Si Fe OC P Cy2 5

Fe-Si-P to Fe-P-Si

Mechanisms of rearrangement
Formation of 2 is straightforward:
Fe SiMe2 OC OC PPh2 1 h - CO Fe SiMe2 OC PPh2 SiMe2 P Ph2

Fe OC 2

For its rearrangement, they draw parallels with silyl(silylene) R2 R2 chemistry: SiR2 1,3 SiR2 1,2 Si R Si M M M M Si R Si R SiR2 R2 R2
the 1,3-migration is unusual, the 1,2-migration can be seen as 1,1-insertion or as reductive elimination

SiR3

Fe-Si-P to Fe-P-Si

Mechanisms of rearrangement
Proposed formation of 3:
Me Si 2 SiMe2 SiMe2Ph

Fe

Fe Fe P 1,3-shift PPh Ph2 1,1-deins P Ph Ph 2 CO Fe P Ph 3 SiMe2Ph CO Fe P Ph SiMe2Ph

1,1-ins

Fe-Si-P to Fe-P-Si

Mechanisms of rearrangement
Proposed formation of 4:
H Fe
ox add P Si Me2 Ph

Fe
red el P Si Me 2 Ph

Fe P SiMe 2 H Ph 4

Fe-Si-P to Fe-P-Si

Difference between Ph and Cy

Cy more bulky, opposes transfer to Si Ph has "more nucleophilic p-electrons" (whatever that means), should make transfer easier There is precedent for transfer of OR from phosphite to silylene, but this is the first example of transfer from phosphide

Fe-Si-P to Fe-P-Si

Relevance
Silylenes exhibit relatively high tendencies to group migration This extends such work to neighbour phosphorus Migrations of organic groups between non-transition-metal elements are relatively rare. Understanding them better can benefit organic synthesis and building of inorganic polymers

10

Fe-Si-P to Fe-P-Si

Evaluation
Correctness: Looks OK, X-rays for most structures, in particular for Phmigrated structure 3 Where doubt remains (structure of 4), alternative structure mentioned No outrageous general claims anywhere Significance: Fairly limited, these are exotic combinations of ligand groups precisely because of their easy rearrangements Apart from the PSi Ph transfer, not much new chemistry The idea of metallacyclopropanes reacting as (phosphide)(silylene) complexes is interesting and perhaps more general
11
Fe-Si-P to Fe-P-Si

Evaluation
Presentation Very clear and to the point Not speculative at all, maybe too limited Terrible title!

Is this a JACS paper ? Not for its general relevance Possibly for its nice science I would have suggested Organometallics

12

Fe-Si-P to Fe-P-Si