Reactivity of half-sandwich metal complexes with sterically encumbered N,N′-bis(2,6-diisopropylphenyl) group-substituted carboranylamidinate ligands

• Published in: Russian chemical bulletin Vol. 63; no. 4; pp. 963 - 969
• Main Authors: Xu, B., Yao, Z. -J., Jin, G. -X.
• Format: Journal Article
• Language: English
• Published: Boston Springer US 01-04-2014
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Full Articles; Inorganic Chemistry; Organic Chemistry; steric effects; electronic effects; diisopropylphenyl carbodiimide; carboranylamidinate; metallation
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-014-0534-6

Reactions of [Cp*MCl
2
]
2
(Cp* is η
5
-C
5
Me
5
, M = Ir, Rh) with carboranylamidinate ligand Cab
N
H (
1a
) (Cab
N
H is 1-R
1
-1,2-C
2
B
10
H
11
, R
1
= (DippNH)C(=NDipp), Dipp is diisopropylphenyl) in the presence of the BuLi excess produced 16-electron half-sandwich iridium and rhodium complexes Cp*M(Cab
N
-Dipp) (
2a
,
b
) (Cab
N
-Dipp is (DippN)C(=NDipp)(
closo
-1,2-C
2
B
10
H
10
), M = Ir (
a
), Rh (
b
)). Unexpected neutral
closo
-metallacarboranes
closo
-[1-R
2
-3-(η
5
-Cp*)-3,1,2-MC
2
B
9
H
10
] (
3a
,
b
) (R
2
= (NHDipp)C(=NDipp), M = Ir (
a
), Rh (
b
)) were prepared by the reaction of the deboronated zwitterionic ligand Dcab
N
H (
1b
) (Dcab
N
H is
nido
-7-[C(NHR
3
)
2
]
+
[7,8-C
2
B
9
H
11
]
−
, R
3
= Dipp) with [Cp*MCl
2
]
2
. All compounds were fully characterized by elemental analysis, IR spectroscopy, mass spectrometry, and NMR spectroscopy. Structures of compounds
1a
,
b
and
3a
,
b
were confirmed by single crystal X-ray diffraction.