This paper describes the synthesis and selected reactions of a series of crystalline mono(β-diiminato)yttrium chlorides 3a, 3b, 4a, 4b, 5a, 5b, 5c and 9. The X-ray structure of each has been determined, as well as of [YCl(L44)2] (6), [Y(L11)2OBut] (7) and [Y{CH(SiMe3)2}(thf)(μ-Cl)2Li(OEt2)2(μ-Cl)]2 (8). The N,N′-κ2-β-diiminato ligands were [{N(R)C(Me)}2CH]− [R = C6H4Pri-2 (L11); R = C6H4But-2 (L22); R = C6H3Pri2-2,6 (L33)], [{N(SiMe3)C(Ph)}2CH)]− (L44) and [{N(C6H3Pri2-2,6)C(H)}2CPh]− (L55). Equivalent portions of Li[Lx] and YCl3 in Et2O under mild conditions yielded [Y(μ-Cl)(Lx)(μ-Cl)2Li(OEt2)2]2 [Lx = L11 (3a) or L22 (3b)] and [Y(μ-Cl)(L33)(μ-Cl)Li(OEt2)2(μ-Cl)]2 (4a) or its thf (instead of Et2O) equivalent 4b. Each of the Li(OEt2)2Cl2 moieties is bonded in a terminal (3) or bridging (4) mode with respect to the two Y atoms; the difference is attributed to the greater steric demand of L33 than L11 or L22. Under slightly more forcing conditions, YCl3 and Li(L22) (via3b) gave the lithium-free complex [YCl2(L22)(thf)2] (5b). Two isoleptic compounds 5a and 5c (having in place of L22 in 5b, L33 and L55, respectively) were obtained from YCl3 and an equivalent portion of K[L33] and Na[L55], respectively; under the same conditions using Na[L44], the unexpected product was [YCl(L44)2] (6) (i.e. incorporating only one half of the YCl3). A further unusual outcome was in the formation of 8 from 3a and 2 Li[CH(SiMe3)2]. Compound [Y(L55){N(H)C6H3Pri2-2,6}(thf)(μ3-Cl)2K]2·4Et2O (9), obtained from 5c and K[N(H)C6H3Pri2-2,6], is noteworthy among group 3 or lanthanide metal (M) compounds for containing MClKCl (M = Y) moieties.