Three procedures were developed for the preparation of Cp2ZrH{(mu-H)(2)BC4H8}, 1. It can be prepared from the reaction of Cp2ZrCl2 with K[H2B2(mu-H)(mu-C4H8)(2)] in a 1:2 molar ratio; the reaction of Cp2ZrCl{(mu-H)(2)BC4H8} with K[H2B2(mu-H)(mu-C4H8)(2)] in a 1:1 molar ratio; and the reaction of Cp2ZrCl{(mu-H)(2)BC4H8} with LiH in a 1:1 molar ratio. Although the first and second procedures imply the possible synthesis of Cp2Zr{(mu-H)(2)BC4H8}(2), this compound is not formed. The preferential formation of 1 instead of Cp2Zr{(mu-H)(2)BC4H8}(2) is probably due to greater thermal stability of 1. The benzyl-substituted compounds, Cp2Zr(CH2Ph){(mu-H)(2)BC4H8}, 2, and Cp2Zr(CH2Ph){(mu-H)(2)BC5H10}, 3, were prepared from the reactions of Cp2ZrCl(CH2Ph) with [H2BC4H8](-) and [H2BC5H10](-), respectively. This preparative route eliminates the side reaction observed in the direct alkylation of zirconocene organohydroborate complexes. The structures of 1-3 are also reported. Crystal data for 1: space group Pnam, a = 9.836(2) Angstrom, b = 10.186(2) Angstrom, c = 13.393(3) Angstrom, Z = 4. Crystal data for 2: space group Pbca, a = 8.3882(10) Angstrom, b = 16.6669(10) Angstrom, c = 27.0063(10) Angstrom, Z = 8. Crystal data for 3: space group P2(1)/n, a = 9.674(2) Angstrom, b = 14.047(2) Angstrom, c = 14.512(3) Angstrom, beta = 102.53(2)degrees, Z = 4.