The nitrene OsF5(NCl)

Journal of Fluorine Chemistry, 30 Received:

August

PRELIMINARY

29, 1985; accepted:

September

469 16, 1985

NOTE

The Nitrene

0sF5(NC1)

R. W. COCKMAN

Department

(1986) 469-470

and R. D. PEACOCK

University

of Chemistry,

of Leicester,

Leicester

LEl 7RH (U.K.)

SUMMARY

Reaction

between

0sF6 and

(CH3)3Si(NCO),

product

with ClF3, y ields a mixture

nitrene

is purified

Recently ReF5(NF)

and ReF5(NCl)

Here we report

[ll.

which contains

by recrystallisation

the nitride

fluoride

by oxidation

OsF5(NCl).

from anhydrous

ReNFq andthe

were prepared

the synthesis

followed

of a novel nitrene

The

HF.

nitrene

and characterised

of the

derivatives in this laboratory

fluoride

of osmium,

OsF5 (NCl). Osmium

hexafluoride

reacts with

to give a dark oily product which

is believed

OsF5(NCO) gaseous excess

(%loOmm)

Treatment (CAUTION)

solidifies

dynamic

after vacuum

remaining

evaporation

to contain

leads to a brown

puce coloured

139/86/$3.50

to a brown

solid which

sublimate

of

dissolves

a red-brown

After warming

solid has a prominent

solid such as

small quantities

from which

of a yellow

113 solution

isocyanato-derivatives

with successive

of the solvent.

a small proportion

in Genetron

on standing

of liquid ClF3 to give a red solution

isolated

0022-l

on i-r. evidence

or 0sF4(NCO).

C1F3

which

(CH3)3Si(NCO)

a

the

i.r. peak at 1215 cm

0 Elsevier Sequoia/Printed

solid is

to 85" under

appears;

in

-1

, and

in The Netherlands

-

470 shows a mass spectral + well as Cl 2.

pattern

which includes

The puce solid dissolves

the solution

yields

the red crystals

white,

includes

orange Os03N+

in anhydrous

and red crystals. and Os02N+

strong peak at 69, which may be assigned frequencies

at 1301(m),

with OS-O and OS-F. crystals

have been identified

OSF~(NC~)

OsFnN

characteristic

mass spectrometer. and at 660(vs) OsF5(NCl)

2'

The IR spectrum (vs,br)

is much less volatile

The compound

We are grateful

(1982) 958

.

of a

; the JR spectrum shows

5

associated The white

(NCl), corresponding

air sensitive

solid which gives a mass

the ions OsF4(NCl)+, In addition

OsF3(NCl)+,

strong peaks appear

(n = 4 to 0) from hydrolysis

shows frequencies (OS-F), 495(w)

in contrast

to the SERC for financial

and D. R. Russell,

in the

at 1215 cm -l(m)

(OS-N),

(TN-Cl) and 425(w).

but the most striking to the purple

to be stable to at least the melting

R. D. Peacock

J. Fawcett,

and, interestingly

(OS-N), and others

than ReF5(NCl),

of a strong colour,

appears

of

The mass spectrum

'nitrene' OsF

(n = 4 to 0).

as well as 0~0,

(OS-F), 625

is the absence

1

as the new

ion OsF5(NCl)+,

and OsFn

of Cl

+

HF and evaporation

has not yet been characterised.

is a white,

the parent

(n = 4,3,2),

to CF3

and OsF N+ as 3

[ll.

(rap. 170-4")

showing

peaks,

(CF) 1210(m),

This product

to the known ReF5(NCl)

spectrum

1290(w)

the ions OsF4N+

feature

Re compound.

point.

support.

J. Chem. Sot.

(Chem. COIWnun.1,