The cup product in Hochschild cohomology is graded commutative for all unitary algebras. If is an -bimodule, then the cohomology with values in is a symmetric graded bimodule over .
(If itself is also an algebra such that its multiplication map is a map of -bimodules, then in general is not commutative (for example, take to be the ground field, and to be an arbitrary non-commutative algebra! I do not know of a criterion for commutatitivity in this case)
These results originally appeared in [M. Gerstenhaber, The cohomology structure of an associative ring, Ann. of Math. (2) 78 (1963), 267–288.], and they are discussed at length in [Gerstenhaber, Murray; Schack, Samuel D. Algebraic cohomology and deformation theory. Deformation theory of algebras and structures and applications (Il Ciocco, 1986), 11--264, NATO Adv. Sci. Inst. Ser. C Math. Phys. Sci., 247, Kluwer Acad. Publ., Dordrecht, 1988.] Both references give proofs of a rather computational nature.
You can find an element-free proof of the graded commutativity in this paper, which moreover applies to the cup-products of many other cohomologies.
As for what happens with non-unital algebras, I do not know. But they are very much used today as they were before. One particular context in which they show up constantly is in the intersection of K-theory and functional analysis, where people study `algebras' which are really just ideals in rings of operators of functional spaces---one egregius example is the algebra of compact operators in a Hilbert space.
By the way, you say that group cohomology is a special case of Hochschild cohomology: it is only in a sense... There is a close relationship between the group cohomology of a group , and the Hochschild chomology of the group algebra, but they are not the same. You can use the second to compute the first (because more generally if and are -modules, then , where on the right we have Hochschild cohomology of the group algebra with values in the -bimodule ), but the «principal» group cohomology is only a little part of the «principal» Hochschild cohomology .
Finally, in the paper by Sletsjøe the definition for the boundary is given as you say because he only considers commutative algebras and only principal coefficients, that is .
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