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New ruthenium complex 3,3-(Ph
2
P(CH
2
)
4
PPh
2
)-3-H-3-Cl-9-Me-
closo-
3,1,2-RuC
2
B
9
H
10
(
1
) and its derivatives 3,3-(Ph
2
P(CH
2
)
4
PPh
2
)-3-Cl-9-Me-
closo-
3,1,2-RuC
2
B
9
H
10
(
2
), 3,3,8-(Ph
2
P(CH
2
)
4
PPh-μ-
(
3
), and 3,3,4,8-(Ph
2
P(CH
2
)
4
P-μ-
(
4
) have been prepared from
nido
-carborane ligand [5-Me-7,8-C
2
B
9
H
11
]
–
containing methyl substituent in the lower belt of basket. The obtained substituted ruthenacarboranes retain geometries and steric configurations of the metal atom typical of unsubstituted analogs, but are characterized by lower values of the Ru(II)–Ru(III) redox potential. The high efficiency of the resulting derivatives as catalysts for controllable methyl methacrylate radical polymerization has been shown.