Hydrocarbyl complexes, ((t)Bu(3)SiNH)(3)ZrR (1-R), were prepared via metatheses of ((t)Bu(3)SiNH)(3)ZrCl (1-Cl) with RMgX or RLi (R = Me, Et, Cy, CH(2)Ph, allyl, CH=CH2, Ph, CH(2)(t)Bu, C=CPh, C=C(t)Bu), through addition of isobutylene, H2C=C=CMe(2), and acetylene to 1-H (R = (i)Bu, dma, or CH=CH2), and by CH-bond activation; thermal 1,2-RH-elimination from 1-R produced putative ((t)Bu(3)SiNH)(2)Zr=NSi(t)Bu(3) (2), which was subsequently trapped by R’H. Thermolysis of 1-R (similar to 100 degrees C, R = Me or Cy) in the presence of H-2, c-C3H6, and CH4 in cyclohexane or neat C6H6, mesitylene, and toluene afforded 1-R (R = ii, Pr-c, Me, Ph, CH2-3,5-Me(2)C(6)H(3)) and a mixture of 1-CH(2)Ph and 1-C(6)H(4)Me, respectively. Exposure of 1-Cy to C2H4 or C6H6 in cyclohexane provided 1-CH=CH2 or 1-Ph, respectively, but further reaction produced 1(2)-(trans-HC=CH) and 1(2)-(p-C6H4) through double CH-bond activation. Thermolysis of ((t)Bu(3)SiND)(3)ZrCH3 (1-(ND)(3)-CH3) in C6H6 or C6D6 yielded CH3D, and 1C(6)H(5) or 1-(ND)(3)C6D5, through reversible benzene activation. Thermolysis of l-Cy in neat cyclohexane, and with C2H6 Or CMe(4) present, gave cyclometalation product ((t)Bu(3)SiNH)(2)ZrNHSi(t)Bu(2)CMe(2)CH(2) (3) and 1-NHSi(t)Bu(3).