Synthesis and Characterization of (Tris(3,5-dimethylpyrazolyl)borato)rhodium Alkyl and Vinyl Chloride Complexes

A series of complexes of the type
Tp‘Rh(CNCH2CMe3)(R)Cl,
where R = CH3, CD3, n-propyl,
isopropyl,
cyclopropyl, and vinyl and Tp‘ =
tris(3,5-dimethylpyrazolyl)borate have been synthesized and
fully characterized.
The complexes are prepared by reaction of the corresponding
Grignard reagent with
Tp‘Rh(CNCH2CMe3)Cl2,
which in turn is synthesized from
Tp‘Rh(NCCH3)Cl2. The complex
Tp‘Rh(CNCH2CMe3)(isopropyl)Cl
crystallizes
in orthorhombic space group Pbcn (No. 60) with a
= 27.8224(1) Å, b = 14.2541(2) Å,
c = 14.5549(2) Å, Z =
8, and V = 5772.23(9) Å3. The
complex
Tp‘Rh(CNCH2CMe3)(cyclopropyl)Cl
crystallizes in monoclinic space
group P21/c (No. 14) with
a = 9.573(2) Å, b = 18.933(3) Å,
c = 17.873(14) Å, β = 103.70(4)°,
Z = 4, and V
= 3147(3) Å3. The complex
Tp‘Rh(PMe3)Cl2 crystallizes in
monoclinic space group P21/n (No. 14)
with a =
10.9384(6) Å, b = 17.3111(9) Å, c
= 13.5132(7) Å, β = 111.536(1)°, Z = 4,
and V = 2378.5(2) Å3.